on 74th Observatory University of Illinois University Urbana-Champaign at Supported by the YMPOSIUM NTERNATIONAL Molecular I National Radio Astronomy Radio National S Spectroscopy June 17 - 21, 2019

2019 International Symposium on Molecular Spectroscopy 74th

MONDAY June 17 TUESDAY June 18 WEDNESDAY June 19 THURSDAY June 20 FRIDAY June 21 8:30 AM 8:30 AM 8:30 AM 8:30 AM 8:30 AM

Foellinger MA RA Auditorium Plenary Plenary Room 116 TA WA FA Roger Adams Mini-symposium: Astronomy Astronomy Laboratory Astrochemistry/Astrobiology ALMA

Room 100 TB WB FB Noyes Laboratory Mini-symposium: Mini-symposium: Atmospheric Science Non-Covalent Interactions Non-Covalent Interactions Room 1024 TC WC FC Chemistry Annex Clusters/Complexes Instrument/Technique Clusters/Complexes Demonstration Room 217 TD WD FD Noyes Laboratory Radicals Electronic Structure, Potential Radicals Energy Surfaces Room B102 TE WE FE Chemical & Life Fundamental Interest Mini-symposium: Lineshapes, Collisional Sciences High-Harmonic Generation/XUV Effects Room 2079 TF WF FF Natural History Bldg Dynamics and Kinetics Ions Comparing Theory and Experiment LUNCH BREAK AFTERNOON SESSIONS RESUME AT 1:45 PM Room 116 MG TG WG RG Roger Adams Mini-symposium: Mini-symposium: Mini-symposium: Mini-symposium: Laboratory Astrochemistry/Astrobiology ALMA Astrochemistry/Astrobiology ALMA Astrochemistry/Astrobiology ALMA Astrochemistry/Astrobiology ALMA Room 100 MH TH WH RH Noyes Laboratory Mini-symposium: Mini-symposium: Mini-symposium: Mini-symposium: Non-Covalent Interactions Non-Covalent Interactions Non-Covalent Interactions Non-Covalent Interactions Room 1024 MI TI WI RI Chemistry Annex Large Amplitude Motions, Small Molecules Structure Determination Rotational Structure Internal Rotation /Frequencies Room 217 MJ TJ WJ RJ Noyes Laboratory Instrument/Technique Conformers and Isomers Metal Containing Atmospheric Science Demonstration Room B102 MK TK WK RK Chemical & Life Theory and Computation Mini-symposium: Mini-symposium: Mini-symposium: Sciences High-Harmonic Generation/XUV High-Harmonic Generation/XUV High-Harmonic Generation/XUV

Room 2079 ML TL WL RL Natural History Bldg Vibrational Structure Spectroscopy as an Spectroscopy as an Spectroscopy as an /Frequencies Analytical Tool Analytical Tool Analytical Tool ‡Ž ‘‡–‘–Š‡͹Ͷ–Š –‡”ƒ–‹‘ƒŽ ›’‘•‹—‘‘Ž‡ —Žƒ”’‡ –”‘• ‘’› —‡ͳ͹ǦʹͳǡʹͲͳͻ ”„ƒƒǦŠƒ’ƒ‹‰ǡ 

 OnbehalfoftheExecutiveCommittee,Iextendaheartfeltwelcometoallthe attendeesofthe74thSymposiumandwelcomeyoutotheUniversityofIllinoisat UrbanaǦChampaign. TheSymposiumpresentsresearchinfundamentalmolecularspectroscopyand awidevarietyofrelatedfieldsandapplications.Thecontinuedvitalityand significanceofspectroscopyisannuallyreǦaffirmedbythenumberoftalks,their variety,andthefactthatmanyaregivenbystudents.Thesepresentationsarethe heartofthemeetingandaredocumentedbythisAbstractBook.Equallyimportantis theinformationflowingfrominformalexchangesanddiscussions.Asorganizers,we strivetoprovideanenvironmentthatfacilitatesbothkindsofinteractions. Theessenceofthemeetingliesinthescientificdiscussionsandyourpersonal experiencesthisweekindependentofthenumberoftimesthatyouhaveattendedthis meeting.Itisoursincerehopethatyouwillfindthismeetinginformativeand enjoyablebothscientificallyandpersonally,whetheritisyourfirstor50thmeeting.If wecanhelptoenhanceyourexperience,pleasedonothesitatetoasktheSymposium staffortheExecutiveCommittee.

BenMcCall SymposiumChair   SCHEDULEOFTALKS ABSTRACTS   ‘†ƒ›ȋȌǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤͳ ‘†ƒ›ȋȌǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤͶͷ —‡•†ƒ›ȋȌǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤͺ —‡•†ƒ›ȋȌǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤ͹ͷ ‡†‡•†ƒ›ȋȌǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤʹͲ ‡†‡•†ƒ›ȋȌǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤͳ͵ͳ Š—”•†ƒ›ȋȌǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤ͵ʹ Š—”•†ƒ›ȋȌǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤͳͺͷ ”‹†ƒ›ȋ ȌǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤ͵ͻ ”‹†ƒ›ȋ ȌǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤʹͳͶ    ǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤʹ͵ͻ           ͹Ͷ–Š    ‹ ‹ ȋ—‡•†ƒ›Ȍ

 Š‡›’‘•‹—’‹ ‹ ™‹ŽŽ„‡Š‡Ž†‘Tuesdayeveningƒ– ‡„‡””›‘‘•ǤŠ‡ ‘•–‘ˆ–Š‡’‹ ‹ ‹• ‹ Ž—†‡†‹›‘—””‡‰‹•–”ƒ–‹‘ȋƒ–„‡Ž‘™ ‘•––‘•–—†‡–•Ȍǡ•‘–Šƒ–ƒŽŽƒ›ƒ––‡†–Š‡‡˜‡–ǤŠ‡Coblentz Society‹•–Š‡Š‘•–ˆ‘””‡ˆ”‡•Š‡–•ˆ‘”‘‡Š‘—”ǤŽ‡ƒ•‡•‡‡›‘—”’ƒ ‡–ˆ‘”ƒ††‹–‹‘ƒŽ†‡–ƒ‹Ž•Ǥ –‡”ƒ–‹‘ƒŽ†˜‹•‘”›‘‹––‡‡ š‡ —–‹˜‡‘‹––‡‡ — ‡”ƒ””‹‰–‘ǡ—‡‡̵•‹˜‡”•‹–› ‡ ƒŽŽǡŠƒ‹” ‹ Šƒ”†ƒ™‡•ǡ‹••‘—”‹‹˜‡”•‹–›‘ˆ ‹‡ ‡Ƭ‡ Š‘Ž‘‰› ”‹ƒ‡ƒ” ‘ ’‘•‘”•Š‹’ ƒ”›‘—„‡”Ž›ǡ‹˜‡”•‹–›‘ˆ ‡‘”‰‹ƒǡŠƒ‹” ƒƒŽ‘–– •—ƒ —Œ‹‹ǡ‘Š‘—‹˜‡”•‹–› ƒ”›†‡ –‹‡‡ ƒ”ƒ†ǡ‹˜‡”•‹–›‘ˆ‹• ‘•‹Ǧƒ†‹•‘ ‹  Ž—ƒ  ‡ƒ”‡’Ž‡ƒ•‡†–‘ƒ ‘™Ž‡†‰‡–Š‡ƒ›‘”‰ƒ‹œƒ–‹‘•–Šƒ–•—’’‘”––Š‡͹Ͷ–Š›’‘•‹—Ǥ”‹ ‹’ƒŽ ‡•Ǧ™‡ ”ƒ„‘™ǡ‡‹„‹œ‹˜‡”•‹–¡– ƒ‘˜‡” ƒ”–‹ ”—‡„‡Ž‡ ˆ—†‹‰ ‘‡•ˆ”‘–Š‡NationalRadioAstronomyObservatoryȋȌǤ‡ƒŽ•‘ƒ ‘™Ž‡†‰‡–Š‡ ƒ‘”‹‘„ƒ›ƒ•Š‹ǡ‹˜‡”•‹–›‘ˆ‘›ƒƒ ‘ ‹”ƒ–ƒ ƒ›‡ˆˆ‘”–•ƒ† ‘–”‹„—–‹‘•‘ˆTheUniversityofIllinois‹Š‘•–‹‰–Š‡‡‡–‹‰ǡ‹ Ž—†‹‰ϐ‹ƒ ‹ƒŽ ‡Ž‡‡—‰ǡŠ‡”•–‘ŽŽ‡‰‡ ‡•Ž‹‡‘‘‡› ‘–”‹„—–‹‘•ˆ”‘–Š‡‡’ƒ”–‡–•‘ˆŠ‡‹•–”›ǡŽ‡ –”‹ ƒŽƒ†‘’—–‡”‰‹‡‡”‹‰ǡƒ†•–”‘‘›Ǥ ‹‡ ƒ”–Š›ǡ ƒ”˜ƒ”†Ǧ‹–Š•‘‹ƒ‡–‡”ˆ‘”•–”‘’Š›•‹ • ‘•Š—”ƒǦ‡‹• ƒ—”ƒ —Ǧ ‘”†ƒǡƒ”•ŠƒŽŽ‹˜‡”•‹–› ƒ˜‡‘‘ —”‘”’‘”ƒ–‡’‘•‘”•ƒ”‡BristolInstruments,Elsevier/JMS,IdealVacuumProducts,Journalof ‘‹ƒ‡Žƒ†”‹ǡ‹˜‡”•‹–›‘ˆ‘Ž‘‰ƒ  ‡””›‹ŽŽ‡”ǡŠ‹‘–ƒ–‡‹˜‡”•‹–› Ž‡ƒ•‡•‡† ‘””‡•’‘†‡ ‡–‘ PhysicalChemistry/ACS,ƒ†LumibirdȋŠ‡‡™ƒ‡‘ˆ—ƒ–‡ŽǦ‡‘’•›•‰”‘—’ȌǤŽ‡ƒ•‡•‡‡–Š‡„ƒ  ƒƒƒ•ƒ‘‘•‡ǡ‹˜‡”•‹–›‘ˆ”‹–‹•Š‘Ž—„‹ƒ ‡ ƒŽŽ ‘ˆ–Š‹•„‘‘ˆ‘”–Š‡‹”ƒ†˜‡”–‹•‡‡–•Ǥ –Š‘›‡‹Œƒǡƒ–‹‘ƒŽƒ†‹‘•–”‘‘›„•‡”˜ƒ–‘”› –‡”ƒ–‹‘ƒŽ›’‘•‹—‘‘Ž‡ —Žƒ”’‡ –”‘• ‘’› ‡Žƒ‹‡ Š‡ŽŽǡƒšǦŽƒ  •–‹–—–‡ˆ‘”–”— –—”‡ƒ† ‡’ƒ”–‡–‘ˆŠ‡‹•–”› ›ƒ‹ •‘ˆƒ––‡” ͸ͲͲǤƒ–Š‡™•˜‡—‡ –‡˜‡Š‹’ƒǡ‡™‘ŽŽ‡‰‡‘ˆ Ž‘”‹†ƒ ”„ƒƒ ͸ͳͺͲͳ ‹ ƒŽ‡”ǡ‡™ ƒ•–Ž‡‹˜‡”•‹–› ‡Ǧƒ‹Žǣ Šƒ‹”̷‹••Ǥ‹ŽŽ‹‘‹•Ǥ‡†— —Œ‹‡—ǡ‹˜‡”•‹–›‘ˆŽ„‡”–ƒǡƒ•–Šƒ‹” Š––’ǣȀȀ‹••Ǥ‹ŽŽ‹‘‹•Ǥ‡†— Šƒ•Šƒ—ǡ ‡–”‘’—Ž•‹‘ƒ„‘”ƒ–‘”› ‹‰ˆ‡‹Š‘—ǡ —†ƒ‹˜‡”•‹–› ‹‹Ǧ›’‘•‹ƒ

ASTROCHEMISTRYANDASTROBIOLOGYINTHEAGEOFALMA ”‰ƒ‹œ‡†„›LaurentMargulèsȋ‹˜‡”•‹–±‡‹ŽŽ‡Ȍƒ†AnthonyRemijanȋȌǤ ‡ƒ–—”‹‰ †‹• —••‹‘•‘–Š‡ƒ†˜ƒ ‡•Šƒ•ƒ†‡ƒ†™‹ŽŽ„‡ƒ‹‰‹–Š‡•‡ˆ‹‡Ž†•Ǥ–‡ Š‘Ž‘‰›Šƒ• ƒŽ”‡ƒ†›”‡˜‘Ž—–‹‘‹œ‡†–Š‡ˆ‹‡Ž†•ƒ†–Š‡‡š–•‡”‹‡•‘ˆ†‡˜‡Ž‘’‡–’”‘‰”ƒ•™‹ŽŽƒ‡–Š‡ƒ””ƒ› –Š‡‘•–’‘™‡”ˆ—Ž•’‡ –”‘• ‘’‹ ‹•–”—‡–‘–Š‡’Žƒ‡–ˆ‘”ƒ•–”‘ Š‡‹ ƒŽƒ†ƒ•–”‘„‹‘Ž‘‰‹ ƒŽ †‹• ‘˜‡”‹‡•Ǥ ˜‹–‡†’‡ƒ‡”•ǣJesJorgensenȋ‹‡Ž•‘Š” •–‹–—–ȌǡBrettA.McGuireȋȌǡNamiSakai ȋ ȌǡCharlotteVastelȋ •–‹–—–’‘—”Žƒ‡ Š‡” Š‡‡•–”‘’Š›•‹“—‡‡–Žƒ±Ž‘‰‹‡Ȍ  HIGHǦHARMONICGENERATIONANDXUVSPECTROSCOPY ”‰ƒ‹œ‡†„›RobertBakerȋŠ‹‘–ƒ–‡ȌǡScottSayresȋ”‹œ‘ƒ–ƒ–‡Ȍǡƒ†JoshVuraǦWeisȋ ȌǤ ‡ƒ–—”‹‰ƒ†˜ƒ ‡•‹Š‹‰ŠǦŠƒ”‘‹ ‰‡‡”ƒ–‹‘ƒ†–Š‡•’‡ –”‘• ‘’›‹–‡ƒ„Ž‡•ǤŠ‡‹‘‹œƒ–‹‘Ǧ ”‡ ‘ŽŽ‹•‹‘’”‘ ‡••‹–•‡Žˆ‹•ƒ•‡•‹–‹˜‡’”‘„‡‘ˆ•ƒŽŽǦ‘Ž‡ —Ž‡‡Ž‡ –”‘‹ •–”— –—”‡Ǥ —”–Š‡”‘”‡ǡ–Š‡ ’—Ž•‡ ƒ„‡—•‡†ƒ•ƒ‡Ž‡‡–Ǧ•’‡ ‹ˆ‹ ’”‘„‡‘ˆ‡Ž‡ –”‘†›ƒ‹ •ƒ–ˆ‡–‘Ǧ–‘ƒ––‘•‡ ‘†–‹‡• ƒŽ‡•Ǥ ˜‹–‡†’‡ƒ‡”•ǣLouDiMauroȋŠ‹‘–ƒ–‡ȌǡWenLiȋƒ›‡–ƒ–‡ȌǡArvinderSandhuȋ‹˜‡”•‹–›‘ˆ ”‹œ‘ƒȌ  NONǦCOVALENTINTERACTIONS ”‰ƒ‹œ‡†„›HelenLeungȋŠ‡”•–‘ŽŽ‡‰‡ȌǡMarkMarshallȋŠ‡”•–‘ŽŽ‡‰‡Ȍǡƒ†YunjieXu ȋ‹˜‡”•‹–›‘ˆŽ„‡”–ƒȌǤ‘Ǧ ‘˜ƒŽ‡–‹–‡”ƒ –‹‘•Šƒ˜‡’”‘ˆ‘—†‹ˆŽ—‡ ‡‘ Š‡‹ ƒŽƒ†„‹‘Ž‘‰‹ ƒŽ •›•–‡•Ǥ –‡”ƒ –‹‘•‹ Š‹”ƒŽ ‘–ƒ –’ƒ‹”•Šƒ˜‡’”‘˜‹†‡†–Š‡„ƒ•‹•ˆ‘”ƒ‡™‡–Š‘†‘ˆ Š‹”ƒŽƒƒŽ›•‹•Ǥ ‡ƒ”‡ƒŽ•‘’Ž‡ƒ•‡†–‘ƒ ‘™Ž‡†‰‡Amplitude,BrightSpec,JASCO,LightConversionUSA, ‡ˆ‘ —•‘•’‡ –”‘• ‘’‹ ƒ†–Š‡‘”‡–‹ ƒŽ Šƒ”ƒ –‡”‹œƒ–‹‘‘ˆ‘Ǧ ‘˜ƒŽ‡–‘Ž‡ —Žƒ”‹–‡”ƒ –‹‘•ƒ† MonstrSENSE,ƒ†TopticaPhotonicsƒ•‘–”‹„—–‹‰’‘•‘”•Ǥ Š‘™–Š‡› ƒ„‡—–‹Ž‹œ‡†–‘‡š’Ž‘”‡‡™ˆ”‘–‹‡”•Ǥ ˜‹–‡†’‡ƒ‡”•ǣMariaSanzȋ‹‰̵•‘ŽŽ‡‰‡‘†‘Ȍǡ JosephFranciscoȋ‹˜‡”•‹–›‘ˆ‡•›Ž˜ƒ‹ƒȌǡKennethLeopoldȋ‹˜‡”•‹–›‘ˆ‹‡•‘–ƒȌ —”•’‘•‘”•™‹ŽŽŠƒ˜‡‡šŠ‹„‹–•ƒ––Š‡›’‘•‹—ƒ†™‡‡ ‘—”ƒ‰‡›‘—–‘˜‹•‹––Š‡‹”†‹•’Žƒ›•Ǥ ƒ‘”‹œ‡ REGISTRATION(SAMEASIN2018!)  Š‡”‡‰‹•–”ƒ–‹‘†‡•‹•Ž‘ ƒ–‡†‹–Š‡Š‡‹•–”›‹„”ƒ”›‹‘›‡•ƒ„ǡƒ†‹•‘’‡‘—†ƒ›ˆ”‘ͶǣͲͲǦ Š‡–Š”‡‡ƒ‘”‹œ‡•ˆ‘”–Š‡‘•–‘—–•–ƒ†‹‰•–—†‡––ƒŽ•ƒ––Š‡ʹͲͳͺ‡‡–‹‰™‹ŽŽ„‡’”‡•‡–‡†ǤŠ‡ ͸ǣͲͲǡƒ†‘†ƒ›–Š”‘—‰Š ”‹†ƒ›ˆ”‘ͺǣͲͲǦͶǣ͵ͲǤ‡ˆ”‡•Š‡–•™‹ŽŽ„‡ƒ˜ƒ‹Žƒ„Ž‡ˆ”‘ͺǣͲͲ ™‹‡”•ƒ”‡ZaijunChenǡƒšŽƒ  •–‹–—–‡‘ˆ—ƒ–—’–‹ •ǢElijahJansǡŠ‡Š‹‘–ƒ–‡‹˜‡”•‹–›Ǣ ǦͶǣ͵ͲǤ ƒ†ElizabethRylandǡ‹˜‡”•‹–›‘ˆ ŽŽ‹‘‹•ƒ–”„ƒƒǦŠƒ’ƒ‹‰ǤŠ‡ƒ‘”‹œ‡™ƒ• ”‡ƒ–‡†„›ƒ‰”‘—’  ‘ˆ•’‡ –”‘• ‘’‹•–•™Š‘ǡƒ•‰”ƒ†—ƒ–‡•–—†‡–•ǡ„‡‡ˆ‹–‡†ˆ”‘–Š‡‡’Šƒ•‹•‘‰”ƒ†—ƒ–‡•–—†‡– CHEMISTRYLIBRARY ’ƒ”–‹ ‹’ƒ–‹‘ǡ™Š‹ ŠŠƒ•„‡‡ƒ—‹“—‡ Šƒ”ƒ –‡”‹•–‹ ‘ˆ–Š‡›’‘•‹—ǤŠ‹•›‡ƒ”–Š”‡‡‘”‡ƒ‘”‹œ‡  ™‹‡”•™‹ŽŽ„‡•‡Ž‡ –‡†Ǥ Š‡Š‡‹•–”›‹„”ƒ”›™‹ŽŽ„‡–Š‡Š‘‡ˆ‘”‘—”‡‰‹•–”ƒ–‹‘†‡•ƒ†‡šŠ‹„‹–‘”•’ƒ ‡ȋ’Ž—• ‘ˆˆ‡‡ƒ† †‘—–•Ȍƒ‰ƒ‹–Š‹•›‡ƒ”ǤŠ‡Ž‹„”ƒ”›Šƒ•ƒˆ‡™•ƒŽŽ ‘ˆ‡”‡ ‡”‘‘•ǡƒ† ‘ˆ› Šƒ‹”•ȋƒ†„‘‘•ǨȌǤ Š‡ƒ™ƒ”†‹•ƒ†‹‹•–‡”‡†„›ƒ”‹œ‡‘‹––‡‡ Šƒ‹”‡†„› ‡‹ˆ‡”˜ƒ‹Œ‰ƒƒ”†‡ȋ‹˜‡”•‹–›‘ˆ  ƒ‹–‘„ƒȌǡƒ† ‘’”‹•‡†‘ˆ”‘‘•ƒ–‡ȋ‹˜‡”•‹–›‘ˆ‹”‰‹‹ƒȌǢƒ”‹ƒƒœȋ‹‰ǯ•‘ŽŽ‡‰‡‘†‘ȌǢ READYROOM/STATION ƒ ‘„–‡™ƒ”–ȋ‘‡ –‹ —–‘ŽŽ‡‰‡ȌǢƒ†‹™‹‡”ǡȋ—”†—‡‹˜‡”•‹–›ȌǤ›“—‡•–‹‘•‘”•—‰‰‡•–‹‘•  ƒ„‘—––Š‡”‹œ‡•Š‘—Ž†„‡ƒ††”‡••‡†–‘–Š‡‘‹––‡‡Ǥ›‘‡ȋ‡•’‡ ‹ƒŽŽ›’‘•–Ǧ†‘ •Ȍ™‹ŽŽ‹‰–‘•‡”˜‡‘ ‡™‹ŽŽŠƒ˜‡ʹ†‡••‹–Š‡‹„”ƒ”›™‹–Š ‘’—–‡”•–Šƒ–›‘— ƒ—•‡–‘–‡•–›‘—”’‘™‡”’‘‹– ƒ’ƒ‡Ž‘ˆŒ—†‰‡••Š‘—Ž† ‘–ƒ – ‡‹ˆ‡”˜ƒ‹Œ‰ƒƒ”†‡ȋ˜ƒ™‹Œ‰̷ Ǥ—ƒ‹–‘„ƒǤ ƒȌǤ ’”‡•‡–ƒ–‹‘Ǥ ˆ›‘—Šƒ˜‡ƒ›’”‘„Ž‡•ǡ–Š‡•–ƒˆˆƒ––Š‡Dz‡ƒ†›–ƒ–‹‘dzȋ”‹‰Š–‡š––‘”‡‰‹•–”ƒ–‹‘Ȍ ƒ ƒ••‹•–›‘—Ǥ  ‹ŽŽ‡””‹œ‡ INTERNETACCESS/WiǦFi  Š‡‹ŽŽ‡””‹œ‡™ƒ• ”‡ƒ–‡†‹Š‘‘”‘ˆ”‘ˆ‡••‘”‡””›Ǥ‹ŽŽ‡”ǡ™Š‘•‡”˜‡†ƒ• Šƒ‹”‘ˆ–Š‡ ƒ Šƒ––‡†‡‡™‹ŽŽ”‡ ‡‹˜‡ƒŽ‘‰‹ƒ†’ƒ••™‘”†–‘ƒ ‡•• ƒ’—•‹ ‹ȋ ǣ ŽŽ‹‘‹•‡–Ȍƒ•ƒ‰—‡•–Ǥ –‡”ƒ–‹‘ƒŽ›’‘•‹—‘‘Ž‡ —Žƒ”’‡ –”‘• ‘’›ˆ”‘ͳͻͻʹ–‘ʹͲͳ͵ǤŠ‡‹ŽŽ‡””‹œ‡ˆ‘”–Š‡„‡•– Š‹•ƒ ‡•••Š‘—Ž†™‘”‹‘•–Ž‘ ƒ–‹‘•–Š”‘—‰Š ƒ’—•ǤŽ‡ƒ•‡”‡ƒ†–Š‡ –‡”‡– ‡’–ƒ„Ž‡•‡ ’”‡•‡–ƒ–‹‘‰‹˜‡„›ƒ”‡ ‡–Šƒ––Š‡ʹͲͳͺ‡‡–‹‰™‹ŽŽ„‡’”‡•‡–‡†ǤŠ‡™‹‡”ǡAmandaSteberǡ ‘Ž‹ ›„‡Ž‘™Ǥ ȋ‹˜‡”•‹–›‘ˆ ƒ„—”‰Ȍǡ™‹ŽŽ‰‹˜‡ƒŽ‡ –—”‡‘Š—”•†ƒ›Ǥ   AUDIO/VIDEOINFORMATION Š‡‹ŽŽ‡””‹œ‡™‹‡”ƒ†Š‹•‘”Š‡” ‘Ǧƒ—–Š‘”•™‹ŽŽ„‡‹˜‹–‡†–‘•—„‹–ƒƒ”–‹ Ž‡–‘–Š‡ ‘—”ƒŽ‘ˆ  ‘Ž‡ —Žƒ”’‡ –”‘• ‘’›„ƒ•‡†‘–Š‡”‡•‡ƒ” Š‹–Š‡’”‹œ‡Ǧ™‹‹‰–ƒŽǤˆ–‡”’ƒ••‹‰–Š‡‘”ƒŽ”‡˜‹‡™ ƒ Š•‡••‹‘”‘‘‹•‡“—‹’’‡†™‹–ŠƒŽƒ’–‘’ ‘’—–‡”ǡ‘–‘™Š‹ Š’”‡•‡–ƒ–‹‘ˆ‹Ž‡•™‹ŽŽ„‡’”‡ǦŽ‘ƒ†‡† ’”‘ ‡••ǡ–Š‡ƒ”–‹ Ž‡™‹ŽŽƒ’’‡ƒ”‹–Š‡ ‘—”ƒŽ™‹–Šƒ ƒ’–‹‘‹†‡–‹ˆ›‹‰–Š‡’ƒ’‡”™‹–Š–Š‡–ƒŽ–Šƒ– „››’‘•‹—•–ƒˆˆǤ‘•—„‹–›‘—”’”‡•‡–ƒ–‹‘ˆ‹Ž‡ǡ›‘——•–‰‘–‘–Š‡ManagePresentationsŽ‹‘ ”‡ ‡‹˜‡†–Š‡‹ŽŽ‡””‹œ‡Ǥ ‘—”™‡„•‹–‡ƒ†ˆ‘ŽŽ‘™–Š‡‹•–”— –‹‘•ǤŽŽˆ‹Ž‡•—•–„‡•—„‹––‡†„›11:59PMCDTTHEDAY  BEFORE›‘—”’”‡•‡–ƒ–‹‘•‡••‹‘ǤŽŽ•—„‹––‡†ˆ‹Ž‡•™‹ŽŽ„‡Ž‘ƒ†‡†‘–‘–Š‡’”‡•‡–ƒ–‹‘ ‘’—–‡” Š‡ƒ™ƒ”†‹•ƒ†‹‹•–‡”‡†„›ƒ”‹œ‡‘‹––‡‡ Šƒ‹”‡†„›‹‡ ‡ƒ˜‡ǡ‘”›‹˜‡”•‹–›ƒ† ‘‡ŠƒŽˆǦŠ‘—”’”‹‘”–‘–Š‡„‡‰‹‹‰‘ˆ–Š‡•‡••‹‘Ǥ ‘’”‹•‡†‘ˆ–‡’Š‡‘‘‡ȋ—” Šƒ•‡‘ŽŽ‡‰‡ȌǢ‹ Šƒ”†ƒ™‡•ȋ‹••‘—”‹‹˜‡”•‹–›‘ˆ ‹‡ ‡ƒ†  ‡ Š‘Ž‘‰›ȌǢ ‹Œ—‹—ȋ‹˜‡”•‹–›‘ˆ‘—‹•˜‹ŽŽ‡ȌǢƒ”ƒ”•ŠƒŽŽȋŠ‡”•–‘ŽŽ‡‰‡ȌǢ‹ Šƒ‡Ž ƒ”–Š› ACKNOWLEDGMENTS ȋ ƒ”˜ƒ”†Ǧ‹–Š•‘‹ƒ‡–‡”ˆ‘”•–”‘’Š›•‹ •ȌǢ‡„‡ ƒ‡‡„Ž‡•ȋƒ•–‡” ŽŽ‹‘‹•‹˜‡”•‹–›ȌǢ”‹•–‹ƒ  —œœƒ”‹‹ȋ‹˜‡”•‹–›‘ˆ‘Ž‘‰ƒȌǢƒ†‹–‡‹Ž‡ȋ”‹œ‘ƒ–ƒ–‡‹˜‡”•‹–›ȌǤ›“—‡•–‹‘•‘” Š‡›’‘•‹—Šƒ‹”™‹•Š‡•–‘ƒ ‘™Ž‡†‰‡–Š‡Šƒ”†™‘”‘ˆ—‡”‘—•’‡‘’Ž‡™Š‘ƒ†‡–Š‹•‡‡–‹‰ •—‰‰‡•–‹‘•ƒ„‘—––Š‡”‹œ‡•Š‘—Ž†„‡ƒ††”‡••‡†–‘–Š‡‘‹––‡‡Ǥ›‘‡™‹ŽŽ‹‰–‘•‡”˜‡‘ƒ’ƒ‡Ž‘ˆ ’‘••‹„Ž‡Ǥ ‹”•–ƒ†ˆ‘”‡‘•–‹•–Š‡›’‘•‹—‘‘”†‹ƒ–‘”‹”‰‹– ƒŽŽǡ™Š‘Šƒ••‘‘–ŠŽ›ƒ†•‹‰Ž‡Ǧ Œ—†‰‡••Š‘—Ž† ‘–ƒ –‹‡ ‡ƒ˜‡ȋŠ‡ƒ˜‡̷‡‘”›Ǥ‡†—ȌǤ Šƒ†‡†Ž›–ƒ‡ ƒ”‡‘ˆƒŽ‘•–ƒŽŽ‘ˆ–Š‡‡Ž‡ –”‘‹ ƒ†Ž‘‰‹•–‹ ƒŽƒ•’‡ –•‘ˆ–Š‡‡‡–‹‰Ǥ‡ ‘†ƒ”‡‘—”  •›’‘•‹—ƒ••‹•–ƒ–•ǡ‹ Šƒ‡Ž ‡ƒ‹•ǡŠ‹Ž‹’‘ Š‡”‹Žǡ ƒƒ›Šƒ›ƒ†‘”‹›‡ǡ™Š‘Šƒ˜‡Šƒ†Ž‡† ‹—‡”ƒ„Ž‡‹’‘”–ƒ–†‡–ƒ‹Ž•–‘‡•—”‡–Š‡•‡••‹‘•ƒ†‡šŠ‹„‹–‹‘•‰‘™‡ŽŽǤ ™‹•Š–‘ƒ ‘™Ž‡†‰‡–Š‡ ˆ‘”ƒ–‹‘ Š‘•’‹–ƒŽ‹–›‘ˆ–Š‡Š‡‹•–”›‡’ƒ”–‡–ƒ†–Š‡ Š‘‘Ž‘ˆŠ‡‹ ƒŽ ‹‡ ‡•ȋƒ•™‡ŽŽƒ•–Š‡ Š‘‘Ž‘ˆ ‘Ž‡ —Žƒ”ƒ†‡ŽŽ‹‘Ž‘‰›Ȍ‹–‘Ž‡”ƒ–‹‰‘—”–ƒ‡‘˜‡”‘ˆ–Š‡‹”„—‹Ž†‹‰•Ǥ ACCOMMODATIONS    Š‡ Š‡ Ǧ‹ˆ‘”†‘”‹–‘”›ƒ ‘‘†ƒ–‹‘•‹•Ž‘ ƒ–‡†‹‘—•ˆ‹‡Ž† ƒŽŽǡͳʹͳͶ‘—–Š ‹”•––”‡‡–ǡ‘’‡•ƒ– ‘‘‘ƒ–—”†ƒ›ǡ —‡ͳͷ–Šƒ–͵ǣͲͲǤŠ‡†‡•™‹ŽŽ„‡ Ž‘•‡†ˆ”‘ʹǣ͵ͲȂ͸ǣ͵Ͳ‘͸Ȁͳ͸ǡ͸Ȁͳͺǡ ͸Ȁͳͻǡ͸ȀʹͲƒ†͸ȀʹͳǤŠ‡†‡•ƒ–—‰‡– ƒŽŽ™‹ŽŽ„‡•–ƒˆˆ‡†ʹͶȀ͹ǤŠ‡†‡•ƒ–ƒ••ƒŒƒ‹•—•–ƒˆˆ‡†Ǥ ‘–‡Ž‹ˆ‘”ƒ–‹‘‹•Ž‹•–‡†‘–Š‡ ™‡„•‹–‡Ǥ  PARKING  ƒ”‹‰’‡”‹–•ƒ”‡ˆ‘”Ž‘–ͳͶȋƒ’̷‡†‘ˆ„‘‘ȌǤ—” Šƒ•‡’ƒ”‹‰ƒ•’ƒ”–‘ˆ›‘—” Š‡ Ǧ‹ƒ––Š‡ †‘”Ǥ‘—ƒ›’—” Šƒ•‡‡–‡”Šƒ‰Ǧ–ƒ‰•ˆ‘”’ƒ”‹‰‡ƒ”–Š‡‡‡–‹‰”‘‘•ƒ––Š‡”‡‰‹•–”ƒ–‹‘†‡•Ǥ  1 MA. Plenary Monday, June 17, 2019 – 8:30 AM LIABILITY Room: Foellinger Auditorium  Š‡›’‘•‹—ˆ‡‡•‹ Ž—†‡’”‘˜‹•‹‘•ˆ‘”–Š‡‹•—”ƒ ‡‘ˆ’ƒ”–‹ ‹’ƒ–•ƒ‰ƒ‹•–’‡”•‘ƒŽ Chair: Martin Gruebele, University of Illinois at Urbana-Champaign, Urbana, IL, USA ‹Œ—”‹‡•ǡ•‹ ‡••ǡ–Š‡ˆ–ǡ‘”’”‘’‡”–›†ƒƒ‰‡Ǥƒ”–‹ ‹’ƒ–•ƒ† ‘’ƒ‹‘•ƒ”‡ƒ†˜‹•‡†–‘‘„–ƒ‹ ™Šƒ–‡˜‡”‹•—”ƒ ‡–Š‡› ‘•‹†‡”‡ ‡••ƒ”›ǤŠ‡›’‘•‹—‘”‰ƒ‹œ‹‰ ‘‹––‡‡ǡ‹–••’‘•‘”•ǡƒ† ‹†‹˜‹†—ƒŽ ‘‹––‡‡‡„‡”•ƒ••—‡ƒ›”‡•’‘•‹„‹Ž‹–›ˆ‘”Ž‘••ǡ‹Œ—”›ǡ•‹ ‡••ǡ‘”†ƒƒ‰‡• Welcome 8:30 –‘’‡”•‘•‘”„‡Ž‘‰‹‰•ǡŠ‘™‡˜‡” ƒ—•‡†ǤŠ‡•–ƒ–‡‡–•ƒ†‘’‹‹‘••–ƒ–‡††—”‹‰‘”ƒŽ’”‡•‡–ƒ–‹‘• Feng Sheng Hu, Dean of the College of Liberal Arts & Sciences ‘”‹™”‹––‡ƒ„•–”ƒ –•ƒ”‡•‘Ž‡Ž›–Š‡ƒ—–Š‘”̵•”‡•’‘•‹„‹Ž‹–‹‡•ƒ††‘‘–‡ ‡••ƒ”‹Ž›”‡ˆŽ‡ ––Š‡‘’‹‹‘• University of Illinois at Urbana-Champaign ‘ˆ–Š‡‘”‰ƒ‹œ‡”•Ǥ MA01 8:40 – 9:20  LASER COOLING OF MOLECULES: TOWARDS ULTRACOLD SYMMETRIC AND CHIRAL SPECIES, INTERNETACCEPTABLEUSEPOLICY John M. Doyle MA02 9:25 – 10:05 ƒ Šƒ––‡†‡‡™‹ŽŽ”‡ ‡‹˜‡ƒŽ‘‰‹ƒ†’ƒ••™‘”†–‘ƒ ‡•• ƒ’—•‹ ‹ȋ ǣ ŽŽ‹‘‹•‡–Ȍƒ•ƒ‰—‡•–Ǥ PROTEIN CHARACTERIZATIONS BY CHIRAL VIBRATIONAL SUM FREQUENCY GENERATION SPEC- —‡•–ƒ ‘—–•ƒ”‡‹–‡†‡†–‘•—’’‘”–ƒ„”‘ƒ†”ƒ‰‡‘ˆ ‘—‹ ƒ–‹‘•Ǥ”‘ˆ‡••‹‘ƒŽƒ†ƒ’’”‘’”‹ƒ–‡ TROSCOPY , Elsa Yan ‡–‹“—‡––‡‹•”‡“—‹”‡†Ǥ‘›‘—•ƒ ‡••ƒ†’‘•–‹‰–Š”‘—‰Š‰—‡•–ƒ ‘—–•‹•ˆ‘”„‹††‡ǤŽŽ—•‡”•—•– Intermission ƒ ‡’––Šƒ––Š‡‹”‹†‡–‹–›ƒ›„‡ƒ••‘ ‹ƒ–‡†™‹–Šƒ› ‘–‡––Š‡›’”‘˜‹†‡™Š‹Ž‡—•‹‰–Š‡•‡”˜‹ ‡Ǥ› ƒ ‡••‹‰–Š‡ ƒ’—•‹ ‹‡–™‘”ǡ›‘—‡š’”‡••Ž›ƒ ‘™Ž‡†‰‡ƒ†ƒ‰”‡‡–‘–Š‡ˆ‘ŽŽ‘™‹‰ǣ MA03 10:40 – 11:20  THE RENAISSANCE OF ROTATIONAL SPECTROSCOPY: THEORY MEETS EXPERIMENT FOR NEW CHAL- •‡‘ˆ–Š‡‰—‡•–ƒ ‘—–•‡”˜‹ ‡‹•ƒ–›‘—”•‘Ž‡”‹•ƒ†–Š‡‡–‹”‡”‹•ƒ•–‘•ƒ–‹•ˆƒ –‘”›“—ƒŽ‹–›ƒ† LENGES, Cristina Puzzarini ’‡”ˆ‘”ƒ ‡‹•™‹–Š›‘—Ǥ‘—ƒ‰”‡‡‘––‘—•‡–Š‡‰—‡•–ƒ ‘—–‹–‡–‹‘ƒŽŽ›‘”—‹–‡–‹‘ƒŽŽ›–‘ ˜‹‘Žƒ–‡ƒ›ƒ’’Ž‹ ƒ„Ž‡Ž‘ ƒŽǡ•–ƒ–‡ǡƒ–‹‘ƒŽ‘”‹–‡”ƒ–‹‘ƒŽŽƒ™ǡ‹ Ž—†‹‰ǡ„—–‘–Ž‹‹–‡†–‘ǡƒ› FLYGARE AWARDS 11:25 ”‡‰—Žƒ–‹‘•Šƒ˜‹‰–Š‡ˆ‘” ‡‘ˆŽƒ™Ǥ‘–Š‡‡š–‡–‘–’”‘Š‹„‹–‡†„›Žƒ™ǡ‹‘‡˜‡–•ŠƒŽŽ–Š‡—‹˜‡”•‹–› Introduction by Yunjie Xu, University of Alberta „‡Ž‹ƒ„Ž‡ˆ‘”’‡”•‘ƒŽ‹Œ—”›ǡ‘”ƒ›‹ ‹†‡–ƒŽǡ•’‡ ‹ƒŽǡ‹†‹”‡ –‘” ‘•‡“—‡–‹ƒŽ†ƒƒ‰‡•™Šƒ–•‘‡˜‡”ǡ ‹ Ž—†‹‰ǡ™‹–Š‘—–Ž‹‹–ƒ–‹‘ǡ†ƒƒ‰‡•ˆ‘”Ž‘••‘ˆ’”‘ˆ‹–•ǡŽ‘••‘ˆ†ƒ–ƒǡ„—•‹‡••‹–‡””—’–‹‘‘”ƒ›‘–Š‡” MA04 11:30 – 11:45 ‘‡” ‹ƒŽ†ƒƒ‰‡•‘”Ž‘••‡•ǡƒ”‹•‹‰‘—–‘ˆ‘””‡Žƒ–‡†–‘›‘—”—•‡‘”‹ƒ„‹Ž‹–›–‘—•‡–Š‡‰—‡•–ƒ ‘—–ǡ MICROWAVE SPECTROSCOPY AT MISSOURI S&T, G. S. Grubbs II Š‘™‡˜‡” ƒ—•‡†ǡ”‡‰ƒ”†Ž‡••‘ˆ–Š‡–Š‡‘”›‘ˆŽ‹ƒ„‹Ž‹–›ȋ ‘–”ƒ –ǡ–‘”–‘”‘–Š‡”™‹•‡Ȍƒ†‡˜‡‹ˆ–Š‡ —‹˜‡”•‹–›Šƒ•„‡‡ƒ†˜‹•‡†‘ˆ–Š‡’‘••‹„‹Ž‹–›‘ˆ•— Š†ƒƒ‰‡•ǤŠ‡—•‡‘ˆ–Š‡‰—‡•–ƒ ‘—–‹••—„Œ‡ –ǡ MA05 11:50 – 12:05 ELECTRONIC SPECTROSCOPY OF MASS-SELECTED LIGAND-PROTECTED METAL NANOCLUSTERS, „—–‘–Ž‹‹–‡†–‘ǡƒŽŽ‹˜‡”•‹–›’‘Ž‹ ‹‡•ƒ†”‡‰—Žƒ–‹‘•†‡–ƒ‹Ž‡†ƒ––Š‡ƒ’—•†‹‹•–”ƒ–‹˜‡ƒ—ƒŽ Christopher J. Johnson ȋŠ––’ǣȀȀ™™™Ǥ ƒǤ‹ŽŽ‹‘‹•Ǥ‡†—ȌǤ‡‡–Š‡‹˜‡”•‹–›̵•‡„”‹˜ƒ ›‘–‹ ‡ ȋŠ––’ǣȀȀ™™™Ǥ˜’ƒƒǤ—‹ŽŽ‹‘‹•Ǥ‡†—Ȁ’‘Ž‹ ‹‡•Ȁ™‡„̴’”‹˜ƒ ›Ǥ ˆȌˆ‘”ƒŽŽƒ’’Ž‹ ƒ„Ž‡Žƒ™•ƒ†’‘Ž‹ ‹‡•Ǥ  2 3 MG. Mini-symposium: Astrochemistry and Astrobiology in the age of ALMA MH. Mini-symposium: Non-covalent Interactions Monday, June 17, 2019 – 1:45 PM Monday, June 17, 2019 – 1:45 PM Room: 116 Roger Adams Lab Room: 100 Noyes Laboratory Chair: Brett A. McGuire, National Radio Astronomy Observatory, Charlottesville, VA, USA Chair: Mark D. Marshall, Amherst College, Amherst, MA, USA

MG01 1:45 – 2:00 MH01 1:45 – 2:00 THE ATACAMA LARGE MILLIMETER/SUBMILLIMETER ARRAY - FROM EARLY SCIENCE TO FULL OPERA- THE SCIENCE AND HUMANITY OF WILLIAM KLEMPERER, THE EARLY YEARS, Stewart E. Novick TIONS., Anthony Remijan MH02 2:03 – 2:18 MG02 INVITED TALK 2:03 – 2:33 THE SCIENCE AND HUMANITY OF WILLIAM KLEMPERER, THE MIDDLE AND LATER YEARS, EXPLORING THE COMPLEX CHEMISTRY OF EMBEDDED PROTOSTARS, Jes Jorgensen Stewart E. Novick MG03 2:39 – 2:54 MH03 2:21 – 2:36 THE APPLICATION OF MOLECULAR ROTATIONAL SPECTROSCOPY TO ANALYZE REGIO- AND STEREOISO- DETECTION OF CH3CN IN THE ENVELOPE AROUND SAGITTARIUS B2(N), Mitsunori Araki, Shuro Takano, Takahiro Oyama, Nobuhiko Kuze, Kazuhisa Kamegai, Koichi Tsukiyama MERS OF CYCLOHEXENE PRODUCED FROM REACTIONS OF A TUNGSTEN BENZENE COMPLEX, Reilly E. Sonstrom, Jate W. Bernard, Umme H. Hossain, Chris A. Pede, Brooks Pate, Jacob A. Smith, W. Dean Harman MG04 2:57 – 3:12 EXPLORING MOLECULAR COMPLEXITY WITH ALMA (EMOCA): COMPLEX ISOCYANIDES IN SGR B2(N), MH04 2:39 – 2:54 Eric R. Willis, Robin T. Garrod, Arnaud Belloche, Holger S. P. Muller,¨ Karl M. Menten SYNTHESIS, MICROWAVE SPECTRA, X-RAY STRUCTURE AND HIGH-LEVEL CALCULATIONS FOR FORMAMI- Intermission DINIUM FORMATE, Zunwu Zhou, Stephen G. Kukolich, R. Alan Aitken, Michael H. Palmer, Alexandra M. Z. Slawin, Honghao Wang, Adam M Daly, Charlotte Cardinaud MG05 3:51 – 4:06 THE INTERACTION OF COSMIC RAYS WITH GALACTIC CENTER MOLECULAR CLOUDS, Farhad Yusef-Zadeh MH05 2:57 – 3:12 CHIRALITY ASPECTS IN THE DIMERIZATION OF VICINAL DIOLS, Beppo Hartwig,MartinA.Suhm MG06 4:09 – 4:24 AN ALMA SEARCH FOR CHIRAL MOLECULES TOWARD SGRB2(N), Brandon Carroll, Brett A. McGuire, Geoffrey Intermission Blake MH06 3:51 – 4:06 MG07 4:27 – 4:42 CHALCOGEN-BONDED TETRAFLUORO-1,3-DITHIETANE WATER COMPLEX: WHAT DOES IT TAKE TO INVERT + EXTENDING THE MILLIMETER/SUB-MILLIMETER SPECTRUM OF PROTONATED FORMALDEHYDE (H2COH ) THE WATER?, Yan Jin, Xiaolong Li, Qian Gou, Gang Feng, Jens-Uwe Grabow, Walther Caminati FOR COMPARISON TO ASTRONOMICAL DATA, Connor J. Wright, Kevin Roenitz, Jay A Kroll, Susanna L. Widicus MH07 4:09 – 4:24 Weaver THE CHALCOGEN-BONDED COMPLEX H3N...S=C=S CHARACTERIZED BY CHIRPED-PULSE BROADBAND MI- MG08 4:45 – 5:00 CROWAVE SPECTROSCOPY, Eva Gougoula, Chris Medcraft, Ibon Alkorta, Nick Walker, Anthony Legon INTERSTELLAR FORMALDEHYDE - A RETROSPECTIVE, Anthony Remijan, Lewis E. Snyder, Philip Jewell, Frank J Lovas MH08 4:27 – 4:42 MICROWAVE SPECTRA, MOLECULAR GEOMETRIES AND BARRIERS TO INTERNAL ROTATION IN COM- PLEXES OF Ar···C5H7N2 AND H2O···C5H7N2 (WHERE C5H7N2 IS 1-, 2-, 4- OR 5-METHYLIMIDAZOLE), Nick Walker, Eva Gougoula, Chris Medcraft, Juliane Heitkamper¨ MH09 4:45 – 5:00 THE CONFORMATIONAL LANDSCAPE OF PERILLYL ALCOHOL REVEALED BY BROADBAND ROTATIONAL SPECTROSCOPY AND THEORETICAL MODELING, Fan Xie, Nathan A. Seifert, Matthias Heger, Javix Thomas, Wolf- gang Jager,¨ Yunjie Xu MH10 5:03 – 5:18 CHIRAL ANALYSIS OF MOLECULES WITH MULTIPLE CHIRAL CENTERS USING CHIRAL TAG ROTATIONAL SPECTROSCOPY, Reilly E. Sonstrom, Kevin J Mayer, Channing West, Brooks Pate, Luca Evangelisti 4 5 MI. Large amplitude motions, internal rotation MJ. Instrument/Technique Demonstration Monday, June 17, 2019 – 1:45 PM Monday, June 17, 2019 – 1:45 PM Room: 1024 Chemistry Annex Room: 217 Noyes Laboratory Chair: Daniel A. Obenchain, DESY, Hamburg, Hamburg, Germany Chair: Steven Shipman, New College of Florida, Sarasota, FL, USA

MI01 1:45 – 2:00 MJ01 1:45 – 2:00 BARRIERS TO INTERNAL ROTATION IN STRUCTURAL ISOMERS OF METHYLIMIDAZOLE DETERMINED BY NANOPHOTONIC SUPERCONTINUUM-BASED MID-INFRARED DUAL-COMB SPECTROSCOPY, R. Holzwarth, BROADBAND ROTATIONAL SPECTROSCOPY, Eva Gougoula, Chris Medcraft, Juliane Heitkamper,¨ Nick Walker Wolfgang Hansel,¨ Hairun Guo, Wenle Weng, Junqiu Liu, Fan Yang, Camille-Sophie Bres,` Luc Thevenaz,´ Dag Schmidt, Tobias J. Kippenberg MI02 2:03 – 2:18 METHYL GROUP INTERNAL ROTATION AND CHLORINE NUCLEAR ELECTRIC QUADRUPOLE COUPLING IN MJ02 2:03 – 2:18 CHLOROACETONE, Brittany E. Long, Frank E Marshall, G. S. Grubbs II, S. A. Cooke DUAL-COMB UP-CONVERSION DETECTION OF FUNDAMENTAL MOLECULAR TRANSITIONS, Zaijun Chen, Theodor W. Hansch,¨ Nathalie Picque´ MI03 2:21 – 2:36 LESS CONFUSION AND MORE INFORMATION IN NOTATION FOR SYMMETRY GROUPS OF MOLECULES WITH MJ03 2:21 – 2:36 LAMs, Peter Groner FREQUENCY COMB PHASE-LOCKED CAVITY RING-DOWN SPECTROSCOPY, Zachary Reed, Joseph T. Hodges MI04 2:39 – 2:54 MJ04 2:39 – 2:54 VIBRATION-TORSION-ROTATION INTERACTIONS IN MOLECULES WITH A C3v TOP AND Cs FRAME: vt=3,4 HIGH-RESOLUTION SPECTROSCOPY OF POLYAROMATIC HYDROCARBONS WITH A SINGLE MODE TORSIONAL AND C–S STRETCHING VIBRATIONAL STATES OF METHYL MERCAPTAN CH3SH, V. Ilyushin,E. TI:SAPPHIRE LASER DISCIPLINED BY AN OPTICAL FREQUENCY COMB, Masatoshi Misono, Sho Yamasaki, Shunji A. Alekseev, Yan Bakhmat, Olena Zakharenko, Holger S. P. Muller,¨ Frank Lewen, Stephan Schlemmer, Sigurd Bauerecker, Kasahara, Masaaki Baba Christof Maul, Christian Sydow, Elena Bekhtereva MJ05 2:57 – 3:12 Intermission ULTRAFAST 2D SPECTROSCOPY WITH FREQUENCY COMBS: TOWARDS CAVITY-ENHANCED MULTIDIMEN- TIONAL SPECTROSCOPY IN MOLECULAR BEAMS , Parashu R Nyaupane, Walker Manley Jones, Melanie A.R. Reber MI05 3:33 – 3:48 ISOLATED SMALL-AMPLITUDE FUNDAMENTALS EMBEDDED IN A PURE TORSIONAL BATH: FIR AND MW MJ06 3:15 – 3:30 SPECTRA OF THE ν10 VIBRATIONAL MODE AND HOT TORSIONAL BANDS OF ACETALDEHYDE, V. Ilyushin, AN ECHELON-BASED SINGLE SHOT OPTICAL AND TERAHERTZ KERR EFFECT SPECTROMETER, Griffin Mead, E. A. Alekseev, Olga Dorovskaya, Mariia Kalambet, L. Margules,` R. A. Motiyenko, Manuel Goubet, Olivier Pirali, Sigurd Geoffrey Blake Bauerecker, Christof Maul, Christian Sydow, Georg Ch. Mellau, Isabelle Kleiner, Jon T. Hougen Intermission MI06 3:51 – 4:06 MJ07 4:09 – 4:24 FTIR SYNCHROTRON SPECTROSCOPY OF THE LOWER MODES OF METHYL-D3 MERCAPTAN (CD3SH) – 2-CEME AND NOT 2-CEME: MULTI-PULSE TECHNIQUES AS APPLIED TO THE ROTATIONAL SPECTRA OF 2- WHERE IS THE C-S STRETCH?, Craig W. Beaman, Ronald M. Lees, Li-Hong Xu, Brant E. Billinghurst CHLOROETHYL METHYL ETHER AND 1,2-EPOXYBUTANE, Erika Riffe, Erika Johnson, Steven Shipman MI07 4:09 – 4:24 MJ08 4:27 – 4:42 HYDROXYL GROUPS INTERNAL ROTATION IN THE METHANEDIOL MOLECULE. DFT STUDY INCLUDING MEASURING BROADBAND TWO-PHOTON ABSORPTION SPECTRA WITH ACCURATE ABSOLUTE CROSS- DISPERSION INTERACTION., Uladzimir Sapeshka, George Pitsevich, Alex Malevich, Valery Satsunkevich SECTIONS IN SOLUTION, Christopher G. Elles, David A. Stierwalt MI08 4:27 – 4:42 MJ09 4:45 – 5:00 CH3 INTERNAL ROTATION IN 9-METHYLANTHRACENE, Masaaki Baba, Masatoshi Misono, Jon T. Hougen PROGRESS AROUND THE HIGH RESOLUTION HETERODYNE SPECTROMETER OF THE AILES BEAMLINE , MI09 4:45 – 5:00 Olivier Pirali, Zachary Buchanan, Sophie Eliet, Joan Turut, Marie-Aline Martin-Drumel, Francis Hindle, Robin Bocquet, P. VIBRATIONAL SPECIFICITY AND ISOTOPIC DEPENDENCE OF PROTON-TRANSFER DYNAMICS IN ELEC- Roy, Jean-Franc¸ois Lampin, Gael¨ Mouret TRONICALLY EXCITED 6-HYDROXY-2-FORMYLFULVENE, Lidor Foguel, Zachary Vealey, Patrick Vaccaro MJ10 5:03 – 5:18 BUILDING A DATABASE FOR QCL PUMPED FAR-IR LASERS, Zachary Buchanan, Marie-Aline Martin-Drumel, Sophie Eliet, Joan Turut, Gael¨ Mouret, Francis Hindle, Jean-Franc¸ois Lampin, Olivier Pirali 6 7 MK. Theory and Computation ML. Vibrational structure/frequencies Monday, June 17, 2019 – 1:45 PM Monday, June 17, 2019 – 1:45 PM Room: B102 Chemical and Life Sciences Room: 2079 Natural History Chair: Richard Dawes, Missouri University of Science and Technology, Rolla, MO, USA Chair: Paul Raston, James Madison University, Harrisonburg, VA, USA

MK01 1:45 – 2:00 ML01 1:45 – 2:00 4 13 LOW-LYING ELECTRONIC STATES OF C H: NOT SIMPLE, Paul Dagdigian, John F. Stanton C MONO-SUBSTITUTED ISOTOPOLOGUES OF PROPYNE (H3CCCH): INVESTIGATING THE ACETYLENIC CH MK02 2:03 – 2:18 STRETCH PERTURBATION, Kirstin D Doney, Dongfeng Zhao, Harold Linnartz DELTA-COUPLED-CLUSTER METHODS FOR ACCURATE CALCULATIONS OF CORE IONIZATION ENERGIES, Xuechen Zheng, Lan Cheng ML02 2:03 – 2:18 HIGH-RESOLUTION INFRARED SPECTROSCOPY OF A NON-NATIVE FORMIC ACID CONFORMER, MK03 2:21 – 2:36 Kirstin D Doney, Andrew Kortyna, Preston G. Scrape, David Nesbitt CALCULATION AND VISUALIZATION OF THE VIBRONIC EIGENFUNCTIONS OF JAHN-TELLER ACTIVE MOLECULES , Ketan Sharma, Terry A. Miller, John F. Stanton ML03 2:21 – 2:36 HIGH-RESOLUTION MID-IR SPECTROSCOPY OF (E)- AND (Z)-1,3-PENTADIENE USING A QUANTUM CASCADE MK04 2:39 – 2:54 LASER, Minh Nhat Tran, Jacob Stewart UNITARY GROUP APPROACH FOR EFFECTIVE POTENTIALS IN 2D SYSTEMS: APPLICATION TO CARBON SUB- ML04 2:39 – 2:54 OXIDE C3O2, Marisol Rodr´ıguez Arcos, Renato Lemus FIRST HIGH RESOLUTION INFRARED SPECTRA of 1-D1-PROPANE. FIRST ANALYSIS OF THE ν9 A1 TYPE B −1 MK05 2:57 – 3:12 BAND NEAR 358 cm , Stephen J. Daunt, Robert Grzywacz, Colin Western, Walter Lafferty, Jean-Marie Flaud, Richard UNITARY GROUP APPROACH FOR EFFECTIVE POTENTIALS IN 3D SYSTEMS, Renato Lemus, Marisol Rodr´ıguez Hutchings, Brant E. Billinghurst Arcos Intermission MK06 3:15 – 3:30 UNCERTAINTIES IN COMPUTER SPECTROSCOPY FROM MACHINE LEARNING, Nikesh S. Dattani ML05 3:33 – 3:48 HIGH RESOLUTION ANION PHOTOELECTRON SPECTROSCOPY OF OLIGOTHIOPHENE LOW-LYING EXCITED Intermission STATES, Glen K Thurston, Cole R Sagan, Etienne Garand MK07 4:09 – 4:24 ML06 3:51 – 4:06 FIRST-PRINCIPLES STUDY OF INFRARED AND RAMAN SPECTRA OF INTERMEDIATES IN ETHANOL CON- MAPPING THE CONFORMATION SPACE OF α-PROLINE BY MATRIX-ISOLATION IR SPECTROSCOPY COM- VERSION TO ETHYL ACETATE AND HYDROGEN, Ruitao Wu, Lichang Wang BINED WITH NIR LASER INDUCED CONFORMATIONAL CHANGE AND STATE-OF-THE-ART AB INITIO COM- MK08 4:27 – 4:42 PUTATIONS, Anita Schneiker, Tamas Voros, Gyorgy Tarczay, Mohamed Amin Ibrahim, Malgorzata Biczysko CALCULATION OF FRANCK CONDON FACTORS FOR METAL-CONTAINING DIATOMIC MOLECULES OF IN- TEREST TO LASER COOLING USING COUPLED-CLUSTER TECHNIQUES, Hannah Korslund, Lan Cheng, Nikesh S. ML07 4:09 – 4:24 MULTI-FACETED SPECTROSCOPIC STUDY OF THE STRUCTURAL CHANGES ASSOCIATED WITH ELEC- Dattani TRONIC EXCITATION OF METHYL ANTHRANILATE , Karl N. Blodgett, Dewei Sun, Joshua L. Fischer, Edwin Sibert, MK09 4:45 – 5:00 Timothy S. Zwier UNDERSTANDING SOLVENT EFFECT ON THE FLUORESCENCE SPECTRA OF 4-VINYL-N,N-DI(P- TOYLY)ANILINE DERIVATIVES , Thomas T Testoff, Lichang Wang ML08 4:27 – 4:42 MODE-MIXING MATRIX AND THE VIBRATIONAL CO-ASSIGNMENT OF THE ROTATIONAL ISOMERS, MK10 5:03 – 5:18 Yurii Panchenko SIMULATING THE THZ-THZ-RAMAN SPECTRUM OF MOLECULES. APPLICATION TO BROMOFORM., Ioan-Bogdan Magdau, Geoffrey Blake, Thomas F. Miller III ML09 4:45 – 5:00 COMB-LOCKED CAVITY-ASSISTED DOUBLE RESONANCE SPECTROSCOPY (CLCA-DR), Jin Wang, Changle Hu, An-Wen Liu, Cunfeng Cheng, Tian-Peng Hua, Yu Robert Sun, Yan Tan, Shui-Ming Hu ML10 5:03 – 5:18 ALGEBRAIC APPROACH FOR AN ACCURATE SIMULATION OF CO2 RAMAN SPECTRA, Marisol Bermudez´ Montana˜ , Renato Lemus, Miguel Carvajal, Francisco Curro Perez-Bernal´ 8 9 TA. Mini-symposium: Astrochemistry and Astrobiology in the age of ALMA TB. Mini-symposium: Non-covalent Interactions Tuesday, June 18, 2019 – 8:30 AM Tuesday, June 18, 2019 – 8:30 AM Room: 116 Roger Adams Lab Room: 100 Noyes Laboratory Chair: Brian Drouin, California Institute of Technology, Pasadena, CA, USA Chair: Gang Feng, Chongqing University, Chongqing, China

TA01 8:30 – 8:45 TB01 INVITED TALK 8:30 – 9:00 A SIMULTANEOUS FIT OF vt = 0 AND 1 TORSION-WAGGING-ROTATIONAL LEVELS OF METHYLAMINE USING INTERMOLECULAR NON-COVALENT INTERACTIONS REVEALED BY BROADBAND ROTATIONAL SPEC- A HYBRID (TUNNELING AND NON-TUNNELING) HAMILTONIAN FORMALISM , Isabelle Kleiner, Jon T. Hougen, TROSCOPY, M. Eugenia Sanz, S. Indira Murugachandran, Shefali Saxena, Ecaterina Burevschi, Donatella Loru, Isabel Pena,˜ Iwona Gulaczyk, Marek Kreglewski, R. A. Motiyenko, V. Ilyushin Elena R. Alonso, Jackson Tang TA02 8:48 – 9:03 TB02 9:06 – 9:21 DETECTING BRANCHING RATIOS OF CHEMICAL REACTIONS AT ASTROPHYSICALLY RELEVANT TEMPER- THE MICROWAVE SPECTRUM AND MOLECULAR STRUCTURE OF (E)-1-CHLORO-1,2- ATURES USING CHIRPED PULSE MILLIMETER WAVE SPECTROSCOPY IN CONTINUOUS CRESU FLOWS, DIFLUOROETHYLENE–ACETYLENE, Helen O. Leung, Mark D. Marshall Brian M Hays, Theo Guillaume, Thomas Sandow Hearne, Omar Abdelkader Khedaoui, Ilsa Rose Cooke, Divita Gupta, Sebastien D. Le Picard, Robert Georges, Abdessamad Benidar, Ludovic Biennier, Ian R. Sims TB03 9:24 – 9:39 SULFUR HYDROGEN BONDING IN THE OLIGOMERS OF AROMATIC THIOLS, Rizalina Tama Saragi, TA03 9:06 – 9:21 Marcos Juanes, Alberto Lesarri, JoseA.Fern´ andez´ THE ELECTRICAL DISCHARGE PRODUCTS OF MULTI-COMPONENT MIXTURES PROBED BY BROADBAND MILLIMETER-WAVE ROTATIONAL SPECTROSCOPY, Benjamin E Arenas, Amanda Steber, Sebastien´ Gruet, Melanie TB04 9:42 – 9:57 MICROWAVE SPECTRUM AND INTERNAL ROTATION OF THE THIOACETIC ACID – WATER COMPLEX, Schnell Anna Huff, CJ Smith, Kenneth R. Leopold TA04 9:24 – 9:39 SPECTRAL ANALYSIS OF A METHYLAMINE AND OZONE MIXTURE, Jay A Kroll, Samuel Zinga, Susanna L. Widi- Intermission cus Weaver TB05 10:36 – 10:51 TA05 9:42 – 9:57 NON-COVALENT INTERACTIONS IN COMPLEXES OF FLUORINATED AROMATIC RINGS INVESTIGATED BY O(1D) INSERTION REACTIONS FOR THE FORMATION AND SPECTRAL ANALYSIS OF IMPORTANT INTERSTEL- ROTATIONAL SPECTROSCOPY, Sonia Melandri, Assimo Maris, Luca Evangelisti, Imanol Usabiaga, Camilla Calabrese, LAR MOLECULES, Hayley Bunn, Jay A Kroll, Chase P Schultz, Samuel Zinga, Susanna L. Widicus Weaver Weixing Li, Laura B. Favero Intermission TB06 10:54 – 11:09 A CONFORMATIONAL STUDY OF THE ALICYCLIC MUSKS ROMANDOLIDE AND HELVETOLIDE USING TA06 10:36 – 10:51 BROADBAND ROTATIONAL SPECTROSCOPY , Ecaterina Burevschi, M. Eugenia Sanz APPLICATIONS OF H-ATOM QUANTUM-DIFFUSION REACTIONS IN SOLID PARA-HYDROGEN TO ASTRO- CHEMICAL STUDIES: FINDING A MYSTERIOUS LINK BETWEEN INTERSTELLAR ISOCYANIC ACID [HNCO] TB07 11:12 – 11:27 THE MICROWAVE SPECTRUM AND MOLECULAR STRUCTURE OF 1-CHLORO-1- AND FORMAMIDE [H2NC(O)H], Karolina Anna Haupa, Gyorgy Tarczay, Yuan-Pern Lee FLUOROETHYLENE–HYDROGEN CHLORIDE, Laboni Hoque, Helen O. Leung, Mark D. Marshall TA07 10:54 – 11:09 EXPLOITING TUNABLE VACUUM ULTRAVIOLET PHOTOIONIZATION COMBINED WITH REFLECTRON TIME- TB08 11:30 – 11:45 EXPLORING THE BINDING OF METHANOL WITH FURANS, Mariyam Fatima, Cristobal Perez, Daniel A. Obenchain, OF-FLIGHT MASS SPECTROMETRY FOR THE ISOMER-SPECIFIC DETECTION OF COMPLEX ORGANIC Melanie Schnell MOLECULES FORMED VIA INTERACTION OF IONIZING RADIATION WITH MIXED ASTROPHYSICAL ICE ANALOGUES, N. Fabian Kleimeier, Matthew James Abplanalp, Rebecca N. Johnson, Samer Gozem, Ralf Ingo Kaiser TB09 11:48 – 12:03 INTERMOLECULAR INTERACTIONS IN AN AZEOTROPE, Sneha Banerjee, Sohini Sarkar, Pankaj Mandal TA08 11:12 – 11:27 THE MILLIMETERWAVE SPECTRUM OF SUCCINONITRILE, Carlos Cabezas, Celina Bermudez,´ Juan Daniel Gallego, Isabel Tanarro, Jose´ Luis Domenech,´ Victor Jose Herrero, Belen´ Tercero, Rosa Lebron,´ Jesus´ Eduardo Quintanilla, Ana Cristina Soria, Jose Cernicharo TA09 11:30 – 11:45 PHOTOPHYSICS AND ELECTRONIC STRUCTURE STUDIES OF PROTONATION OF QUINOLINE, Hirdyesh Mishra 10 11 TC. Clusters/Complexes TD. Radicals Tuesday, June 18, 2019 – 8:30 AM Tuesday, June 18, 2019 – 8:30 AM Room: 1024 Chemistry Annex Room: 217 Noyes Laboratory Chair: Kaori Kobayashi, University of Toyama, Toyama, Japan Chair: Sang Lee, Pusan National University, Busan, Korea

TC01 8:30 – 8:45 TD01 8:30 – 8:45 MILLIMETER/SUBMILLIMETER DETECTION OF METHANOL CLUSTERS IN A SUPERSONIC EXPANSION A SINGLE LONGITUDIANL MODE OPTICAL PARAMETRIC OSCILLATOR FOR HIGH RESOLUTION SPEC- SOURCE, Kevin Roenitz, Connor J. Wright, Jay A Kroll, Susanna L. Widicus Weaver TROSCOPY OF FREE RADICALS, Qiang Zhang, Deping Zhang, Boxing Zhu, Yang Chen, Dongfeng Zhao TC02 8:48 – 9:03 TD02 8:48 – 9:03 ANALYSIS OF THE ROTATIONAL SPECTRUM OF LARGE DIFLUOROMETHANE CLUSTERS, Luca Evangelisti, THE ELECTRONIC SPECTRUM AND MOLECULAR GEOMETRY OF THE JET-COOLED STIBINO (SbH2)FREE Anna Fiorini, Luca Zerbini, Luca Foschini, Camilla Calabrese, Emilio J. Cocinero, Berhane Temelso, George C Shields, RADICAL, Fumie X Sunahori, Dennis Clouthier, Tony Smith Brooks Pate TD03 9:06 – 9:21 TC03 9:06 – 9:21 INFRARED SPECTRUM OF (Z)-3-IODO-BUT-2-EN-1-YL [•CH2CHC(CH3)I] PRODUCED UPON PHOTODISSOCIA- USING CONCENTRATION DEPENDENCE OF MICROWAVE SPECTRA OF 2-COMPONENT MIXTURES TION OF (Z)-1,3-DIIODO-BUT-2-ENE [(CH2I)HC = C(CH3)I]INSOLIDPARA-HYDROGEN , Karolina Anna Haupa, TO IDENTIFY SINGLE COMPONENT CLUSTERS - APPLICATION TO (FLUOROETHYLENE)n AND (1,1- Yuan-Pern Lee DIFLUOROETHYLENE)n, Rebecca A. Peebles, Sean A. Peebles, Prashansa Kannangara, Tulana Ariyaratne, Brooks Pate, Channing West TD04 9:24 – 9:39 THE HIGH-RESOLUTION ELECTRONIC SPECTRUM OF THE SiCCl FREE RADICAL: PROBING THE CARBON- TC04 9:24 – 9:39 SILICON TRIPLE BOND , Dennis Clouthier, Gretchen K Rothschopf, Tony Smith RELAXATION DYNAMICS OF NEUTRAL IRON OXIDE CLUSTERS USING FEMTOSECOND PUMP-PROBE SPEC- TROSCOPY, Jacob M Garcia, Scott G Sayres Intermission Intermission TD05 10:18 – 10:33 HIGH RESOLUTION IR SPECTROSCOPY OF MONOHALOCARBENES: THE CH STRETCH FUNDAMENTAL AND TC05 10:18 – 10:33 VIBRATIONAL COUPLING IN HCF, Kirstin D Doney, Andrew Kortyna, Preston G. Scrape, David Nesbitt PROGRESSIVE POLARIZATION OF PHENANTHRIDINE WITH INCREASING HYDRATION DEGREE EVIDENCED BY QUADRUPOLE AND ITS COMPARISON WITH FORMAMIDE CLUSTERS, Pablo Pinacho, Amanda Steber, Do- TD06 10:36 – 10:51 EXPERIMENTAL EVIDENCE OF THE ν3 MODE IN NO3 VIA SLOW PHOTOELECTRON VELOCITY-MAP IMAGING natella Loru, Melanie Schnell − OF COLD NO ,MarkCBabin, Jessalyn A. DeVine, John F. Stanton, Daniel Neumark TC06 10:36 – 10:51 3 HIGH-RESOLUTION INFRARED SPECTROSCOPY OF CARBON-SELENIUM CHAINS: SeC3Se and C3Se, TD07 10:54 – 11:09 ˜ 2 Thomas Salomon, Yury Chernyak, John B Dudek, Jurgen¨ Gauss, Stephan Schlemmer, Sven Thorwirth VIBRONIC STRUCTURE OF THE NO3 X A2 SYSTEM, Masaru Fukushima TC07 10:54 – 11:09 TD08 11:12 – 11:27 − − A SPECTROSCOPIC EXPLORATION OF MoMnOy CLUSTERS AS HYDROGEN EVOLUTION CATALYSTS , VIBRATIONAL SPECTROSCOPY OF CS2 RADICAL ANION IN WATER, Ireneusz Janik,G.N.R.Tripathi Abbey McMahon, Carley N Folluo, Jarrett Mason, Caroline Chick Jarrold TD09 Post-Deadline Abstract 11:30 – 11:45 + TC08 11:12 – 11:27 SPECTROSCOPY AND DYNAMICS OF QUANTUM STATE CONTROLLED SIO , Ivan Antonov, Patrick R Stollenwerk, − − MODELING THE PHOTOELECTRON SPECTRA OF CeO2Bx (x=2, 3) AND CeB6 CLUSTERS, Hassan Harb,HrantP Sruthi Venkataramanababu, Brian C. Odom Hratchian TD10 Post-Deadline Abstract 11:48 – 12:03 CAVITY RING-DOWN SPECTROSCOPY OF JET-COOLED YO MOLECULES, Anam C. Paul, Hamzeh Telfah, Xiye Hu, Jinjun Liu 12 13 TE. Fundamental interest TF. Dynamics and kinetics Tuesday, June 18, 2019 – 8:30 AM Tuesday, June 18, 2019 – 8:30 AM Room: B102 Chemical and Life Sciences Room: 2079 Natural History Chair: Jens-Uwe Grabow, Gottfried-Wilhelm-Leibniz-Universitat,¨ Hannover, NI, Germany Chair: Kyle N. Crabtree, University of California, Davis, CA, USA

TE01 8:30 – 8:45 − TF01 8:30 – 8:45 EXTENSIVE HIGH-RESOLUTION PHOTOASSOCIATION SPECTRA AND PERTURBATION ANALYSIS OF 2(0 ) CHARACTERIZATION OF THE HIGHLY DYNAMIC INTERFACE IN THE PLASTOCYANIN-CYTOCHROME fCOM- LONG-RANGE STATE OF ULTRACOLD RbCs MOLECULES , Dianqiang Su, Zhonghua Ji, Yanting Zhao, Chuanliang Li, PLEX BY SITE-SPECIFIC 2D IR, Sashary Ramos, Amanda L Le Sueur, Rachel E. Horness, Megan Thielges Jinjun Liu TF02 8:48 – 9:03 TE02 8:48 – 9:03 PROBING VIBRATIONAL WAVE PACKETS IN ORGANOPHOSHOROUS MOLECULES USING FEMTOSECOND HIGH-RESOLUTION ROTATIONAL SPECTROSCOPY AND COHERENT CONTROL OF CaH+, Chin-wen Chou,Yi- TIME-RESOLVED MASS SPECTROMETRY, Derrick Ampadu Boateng, Katharine Moore Tibbetts heng Lin, Alejandra Collopy, Christoph Kurz, Tara Fortier, Scott Diddams, Dietrich Leibfried, David Leibrandt TF03 9:06 – 9:21 TE03 9:06 – 9:21 ULTRAFAST COHERENT DISSOCIATION DYNAMICS IN NITROTOLUENE RADICAL CATIONS, Derrick Ampadu LAMB DIP MEASUREMENTS OF MOLECULES WITH KHZ ACCURACY IN THE MID-INFRARED, Cunfeng Cheng, Boateng, Katharine Moore Tibbetts Zitan Zhang, Yu Robert Sun, An-Wen Liu, Shui-Ming Hu TF04 9:24 – 9:39 TE04 9:24 – 9:39 CONTROLLING DISSOCIATIVE DOUBLE IONIZATION OF ETHANE WITH ELLIPTICAL POLARIZED STRONG CP-FTMMW SPECTROSCOPY OF HIGH- RYDBERG STATES OF NO, Timothy J Barnum, Jun Jiang, Robert W Field FIELDS, Gihan Basnayake, Duke A. Debrah, Wen Li TE05 9:42 – 9:57 + TF05 9:42 – 9:57 AN INFRARED PHOTODISSOCIATION SPECTROSCOPIC AND THEORETICAL STUDY OF M(CO)6,7,8 (M = Ti, Zr, UF-CRDS: A PULSED UNIFORM FLOW APPARATUS WITH CW-CAVITY-RINGDOWN SPECTROSCOPY , Nicolas Hf), Shujun Lei, Jiaye Jin, Mingfei Zhou Suas-David, Shameemah Thawoos, Arthur Suits TE06 10:00 – 10:15 TF06 10:00 – 10:15 ANOMALOUS ZEEMAN SPLITTING IN THE ROVIBRATIONAL SPECTRUM OF THE OH RADICAL SOLVATED PRODUCT BRANCHING AND LOW TEMPERATURE REACTION KINETICS BY CHIRPED-PULSE FOURIER IN SUPERFLUID HELIUM or: HOW I LEARNED TO STOP WORRYING AND LOVE THE PROVERBIAL DROPLET TRANSFORM MM-WAVE SPECTROSCOPY IN A PULSED UNIFORM SUPERSONIC FLOW, Nureshan Dias, Ritter EFFECTS , Gary E. Douberly Krueger, Nicolas Suas-David, Arthur Suits, Bernadette M. Broderick Intermission Intermission TE07 10:54 – 11:09 TF07 10:54 – 11:09 173 PYROLYSIS OF ETHYL ESTERS IN A MICRO-REACTOR, Cory Rogers, Jessie P Porterfield, John W Daily, FINE AND HYPERFINE STRUCTURE OF YbF , Hailing Wang, Timothy Steimle, Richard Mawhorter, Jens-Uwe Barney Ellison, Nicole Labbe Grabow TE08 11:12 – 11:27 TF08 11:12 – 11:27 AN ELECTRONIC SPECTROSCOPIC STUDY OF A MOLECULAR BEAM SAMPLE OF YbOCH3, Timothy Steimle, NUCLEAR SPIN CONVERSION OF PROPYNE IN SOLID PARAHYDROGEN, Aaron I. Strom, David T. Anderson Anh T. Le, Ephriem Tadesse Mengesha, Benjamin Augenbraun, Zack Lasner, John M. Doyle TF09 11:30 – 11:45 TE09 11:30 – 11:45 THE TEMPERATURE DEPENDENCE OF THE H + N2O REACTION IN SOLID HYDROGEN, Fredrick M. Mutunga, THE BENDING MODES OF YbOH PROBED BY VISIBLE SPECTROSCOPY, Timothy Steimle, Hailing Wang, Ephriem Kelly M. Olenyik, Aaron I. Strom, Kaycee L. Fillmore, David T. Anderson Tadesse Mengesha, Nickolas Pilgram, Nicholas R Hutzler TF10 11:48 – 12:03 TE10 11:48 – 12:03 ULTRACOLD CHEMICAL REACTIONS OF KRb MOLECULES, David Grimes, Yu Liu, Ming-Guang Hu, Andrei Gheo- THEORETICAL STUDY OF ThO AND HfF+ FOR ELECTRON ELECTRIC DIPOLE MOMENT SEARCH EXPERI- rghe, Kang-Kuen Ni MENTS, Alexander Petrov, Leonid Skripnikov, Anatoly Titov 14 15 TG. Mini-symposium: Astrochemistry and Astrobiology in the age of ALMA TH. Mini-symposium: Non-covalent Interactions Tuesday, June 18, 2019 – 1:45 PM Tuesday, June 18, 2019 – 1:45 PM Room: 116 Roger Adams Lab Room: 100 Noyes Laboratory Chair: Isabelle Kleiner, CNRS et Universites´ Paris-Est et Paris Diderot, Creteil,´ France Chair: Anna Huff, University of Minnesota, Minneapolis, MN, USA

TG01 INVITED TALK 1:45 – 2:15 TH01 INVITED TALK 1:45 – 2:15 MOLECULAR DISCOVERY ACROSS THE ALMA BANDS: FROM SALTY DISKS TO COMPLEX MOLECULES AT SPECTROSCOPY OF JUPITER’S ATMOSPHERE: INSIGHTS FROM DFT AND AB-INITIO CALCULATIONS, 900 GHz, Brett A. McGuire Joseph S Francisco, Tarek Trabelsi TG02 2:21 – 2:36 TH02 2:21 – 2:36 THE LABORATORY ROTATIONAL STUDY OF METHYL ISOCYNATE, Zbigniew Kisiel, Lucie Kolesnikova´,ElenaR. UNCOVERING A NEW CLASS OF REACTIONS IN THE ATMOSPHERE: SN2-TYPE SUBSTITUTION REACTIONS Alonso, Jose Cernicharo, J.-C. Guillemin, Jose´ L. Alonso OF NITROGEN OXIDES AND SEAWATER, Laura M McCaslin, Mark Johnson, R. Benny Gerber TG03 2:39 – 2:54 TH03 2:39 – 2:54 LARGE AMPLITUDE MOTION EFFECTS IN THE TPES SPECTRUM OF METHYL ISOCYANATE CH3NCO , O. J. LOCAL MODE APPROACH TO THE CH STRETCH SPECTRA OF DINAPHTHYLETHANES, Angela Ablaberdieva, Harper, B. Gans, S. Boye-P´ eronne,´ L. H. Coudert, J.-C. Loison, G. A. Garcia, J.-C. Guillemin Daniel M. Hewett, Timothy S. Zwier, Edwin Sibert TG04 2:57 – 3:12 TH04 2:57 – 3:12 MICROWAVE-WAVE SPECTROSCOPY OF 5-METHYL HYDANTOIN, Hiroyuki Ozeki, Minami Awatsu, Kaori A PATH FROM GAS TO LIQUID: DEVELOPMENT OF MODEL HAMILTONIANS FOR CONDENSED PHASE LOCAL Kobayashi MODE IR SPECTRA VIA BENZENE (Bz) AND Bz2, Zachary Dyott,EdwinSibert TG05 3:15 – 3:30 Intermission SUBMILLIMETER WAVE SPECTROSCOPY FOR ISM: IMINES WITH INTERNAL ROTATION, L. Margules` ,R.A. Motiyenko, V. Ilyushin, Olga Dorovskaya, Anthony Remijan, Brett A. McGuire, J.-C. Guillemin TH05 3:51 – 4:06 THEORETICAL STUDY OF SURFACE-ENHANCED RAMAN SPECTRA OF WATER AND IONIC COMPLEXES IN Intermission ELECTROCHEMICAL INTERFACES, Ran Pang, De-Yin Wu, Zhong-Qun Tian TG06 4:09 – 4:24 TH06 4:09 – 4:24 THE NANOCOSMOS GAS CELL: A BROADBAND FOURIER TRANSFORM MILLIMETERWAVE SPECTROMETER THE AUTOMATED CONSTRUCTION OF POTENTIAL ENERGY SURFACES SUITABLE TO DESCRIBE VDW COM- BASED ON RADIO ASTRONOMY RECEIVERS, Celina Bermudez´ , Carlos Cabezas, Isabel Tanarro, Jose´ Luis Domenech,´ PLEXES OF HIGHLY EXCITED NASCENT REACTION PRODUCT MOLECULES, Ernesto Quintas Sanchez´ , Richard Victor Jose Herrero, Juan Daniel Gallego, Pablo de Vicente, Felix´ Tercero, Jose´ Antonio Lopez´ Perez,´ Jose Cernicharo Dawes, Kelvin Lee, Michael C McCarthy TG07 4:27 – 4:42 TH07 4:27 – 4:42 THE NANOCOSMOS GAS CELL AS A TOOL FOR SPECTROSCOPY: THE MILLIMETERWAVE SPECTRUM OF N- THE PREDICTION AND OBSERVATION OF VDW COMPLEXES OF HIGHLY VIBRATIONALLY EXCITED CS AND ETHYLFORMAMIDE , Celina Bermudez´ , Carlos Cabezas, Juan Daniel Gallego, Jose´ Manuel Hernandez, Isabel Tanarro, SIS WITH ARGON, Richard Dawes, Ernesto Quintas Sanchez,´ Kelvin Lee, Michael C McCarthy Jose´ Luis Domenech,´ Victor Jose Herrero, Belen´ Tercero, Ana Cristina Soria, Rosa Lebron,´ Jesus´ Eduardo Quintanilla, Jose Cernicharo TH08 4:45 – 5:00 IR-IR PREDISSOCIATION SPECTROSCOPY OF PROTONATED TRIALANINE: BEGINNING TO DETERMINE HOW TG08 4:45 – 5:00 SIDE CHAINS AFFECT STRUCTURE AND SOLVATION, Summer Lee Sherman, Kaitlyn C Fischer, Jonathan Voss, Eti- EXTENDED ANALYSIS OF THE ROTATIONAL SPECTRUM OF METHOXYISOCYANATE IN THE GROUND AND enne Garand LOWEST EXCITED VIBRATIONAL STATES, R. A. Motiyenko, A. Pienkina, L. Margules,` J.-C. Guillemin TH09 5:03 – 5:18 TG09 5:03 – 5:18 COORDINATION AND STRUCTURE OF LATE TRANSITION METAL CATION (Co, Rh, Pt) ACETYLENE COM- + FORMATION OF THE ALMA MOLECULE HOCH2CN AND RELATED SPECIES FROM THE REACTION OF C PLEXES STUDIED WITH INFRARED PHOTODISSOCIATION SPECTROSCOPY, Joshua H Marks, Timothy B Ward, WITH HCN AND HNC IN ICY GRAIN MANTLES, David E. Woon Michael A Duncan TH10 5:21 – 5:36 TRANSFERRING POLARIZABILITIES FROM DIATOMICS TO LARGER MOLECULES, Stephen L Coy,TimothyJ Barnum, Robert W Field, Bryan M. Wong 16 17 TI. Small molecules TJ. Conformers and isomers Tuesday, June 18, 2019 – 1:45 PM Tuesday, June 18, 2019 – 1:45 PM Room: 1024 Chemistry Annex Room: 217 Noyes Laboratory Chair: Dennis W. Tokaryk, University of New Brunswick, Fredericton, NB, Canada Chair: Jennifer van Wijngaarden, University of Manitoba, Winnipeg, MB, Canada

TI01 1:45 – 2:00 TJ01 1:45 – 2:00 JON HOUGEN’S MONOGRAPH NBS 115, Robert W Field HIGH RESOLUTION FAR-INFRARED SPECTROSCOPY OF TRANS- AND GAUCHE-BUTADIENE, Marie-Aline Martin-Drumel, Jessie P Porterfield, Joshua H Baraban, Bryan Changala, Matthew Nava, Manuel Gou- TI02 2:03 – 2:18 1 bet, Pierre Asselin, Pascale Soulard, Robert Georges, Olivier Pirali, Brant E. Billinghurst, John F. Stanton, Michael C DIRECT POTENTIAL FIT FOR THE X Σ STATE OF F2: PERTURBATION OF THE HIGHEST OBSERVED V=22 VIBRATIONAL LEVEL, Robert W Field, John Coxon, Photos Hajigeorgiou McCarthy TI03 2:21 – 2:36 TJ02 2:03 – 2:18 FINE AND HYPERFINE ANALYSIS OF RUTHENIUM MONOBORIDE ISOTOPOLOGUES., Jacob M Dore,AllanG. A STUDY OF THE CONFORMATIONAL ISOMERISM OF N-PROPYL NITRATE BY MICROWAVE SPECTROSCOPY, Adam, Colan Linton, Dennis W. Tokaryk W. Orellana, Susanna L. Stephens, Stewart E. Novick, S. A. Cooke, Carolyn Brauer, Thomas A. Blake TI04 2:39 – 2:54 TJ03 2:21 – 2:36 73 CONFORMATIONAL ISOMERISM OF N-BUTYL NITRATE STUDIED BY MICROWAVE SPECTROSCOPY , ISOTOPE INVARIANT FITTING OF GeO AND GeS AND THE Ge QUADRUPOLE MOMENT DERIVED FROM Susanna L. Stephens, Joshua A. Signore, Carolyn Brauer, Thomas A. Blake, S. A. Cooke, Stewart E. Novick SPECTROSCOPY AND QUANTUM CHEMICAL CALCULATIONS, Sven Thorwirth, Kelvin Lee, Marie-Aline Martin- Drumel, Brett A. McGuire, Florian Kreuter, Franziska Engel, Stella Stopkowicz, Jurgen¨ Gauss, Cristina Puzzarini, Stephan TJ04 2:39 – 2:54 Schlemmer, Michael C McCarthy 1-IODOPENTANE, EXPERIMENTS AND CALCULATIONS, Susanna L. Stephens, Joshua A. Signore, Lan Cheng, William C. Bailey, S. A. Cooke, Stewart E. Novick TI05 2:57 – 3:12 3 HYPERFINE STRUCTURE IN THE (2-0) [18.3]3-X Δ3 TRANSITION OF COBALT MONOBORIDE., Jacob M Dore, Intermission Allan G. Adam, Colan Linton, Dennis W. Tokaryk TJ05 3:33 – 3:48 Intermission DISPERSION-DRIVEN ISOMERISM IN THE GAS PHASE: THEORETICAL AND MICROWAVE SPECTROSCOPIC STUDY OF ALLYL ISOCYANATE , Wenhao Sun, Olamide P. Sogeke, Weslley G. D. P. Silva, Jennifer van Wijngaarden TI06 3:51 – 4:06 FIRST IDENTIFICATION OF A 2Δ STATE OF CaH IN THE VISIBLE REGION., Jin Furuta, Kyohei Watanabe, Iori Tani, TJ06 3:51 – 4:06 Kaori Kobayashi, Yoshiki Moriwaki, Stephen Cary Ross MICROWAVE SPECTROSCOPIC AND THEORETICAL EXAMINATION OF ALLYL ISOTHIOCYANATE CONFOR- MATIONAL SPACE, Joseph Stitsky , Wenhao Sun, Weslley G. D. P. Silva, Jennifer van Wijngaarden TI07 4:09 – 4:24 MICROWAVE SPECTROSCOPY OF OXAZOLE AND ISOXAZOLE, Kaori Kobayashi, Shozo Tsunekawa TJ07 4:09 – 4:24 THE CONFORMATIONAL PANORAMA OF MANDELIC ACID, Lucie Kolesnikova´, Elena R. Alonso, Santiago Mata, TI08 4:27 – 4:42 Jose´ L. Alonso PURE-ROTATIONAL RAMAN AND ELECTRONIC-RAMAN SPECTRUM OF NITRIC OXIDE, Aman Satija, Robert P. Lucht TJ08 4:27 – 4:42 CONFORMATION SPECIFIC SPECTROSCOPY OF AC-γ4-PHE-NHME: RELATIVE ABUNDANCES IN A SUPER- TI09 4:45 – 5:00 HIGH-TEMPERATURE METHANE ABSORPTION WITH A DUAL FREQUENCY COMB SPECTROMETER, SONIC EXPANSION DETERMINED USING IR POPULATION TRANSFER, Joshua L. Fischer, Karl N. Blodgett, Christo- Nathan A Malarich, David Yun, Sean Coburn, Keeyoon Sung, Brian Drouin, Gregory B Rieker pher P Harrilal, Timothy S. Zwier TI10 5:03 – 5:18 TJ09 4:45 – 5:00 THEORY OF NEAR-RESONANT INTRACAVITY ENHANCED TWO-PHOTON ABSORPTION, Kevin Lehmann THE ROLE OF TYROSINE IN STABILIZING GAS PHASE ZWITTERIONIC CONFIGURATIONS OF PEPTIDE IONS REVEALED BY IR-UV DOUBLE RESONANCE SPECTROSCOPY, Christopher P Harrilal, Anthony Pitts-McCoy, Scott A McLuckey, Timothy S. Zwier TJ10 5:03 – 5:18 JET-COOLED, CONFORMER-SPECIFIC IR SPECTRA OF CYCLICALLY-CONSTRAINED β-PEPTIDES. DOES CON- DENSED PHASE STRUCTURE SURVIVE THE VACUUM?, Karl N. Blodgett, Timothy S. Zwier 18 19 TK. Mini-symposium: High-Harmonic Generation and XUV Spectroscopy TL. Spectroscopy as an analytical tool Tuesday, June 18, 2019 – 1:45 PM Tuesday, June 18, 2019 – 1:45 PM Room: B102 Chemical and Life Sciences Room: 2079 Natural History Chair: Josh Vura-Weis, University of Illinois at Urbana-Champaign, Urbana, IL, USA Chair: Brandon Carroll, Harvard-Smithsonian Center for Astrophysics, Cambridge, MA, USA

TK01 1:45 – 2:00 TL01 1:45 – 2:00 WELCOME AND INTRODUCTIONS, Josh Vura-Weis, Robert Baker, Scott G Sayres SAMPLING REQUIREMENTS FOR MIXTURE ANALYSIS USING MOLECULAR ROTATIONAL RESONANCE TK02 2:03 – 2:18 SPECTROSCOPY, Justin L. Neill, Alex Mikhonin, Matt Muckle, Roger L Reynolds UNDERSTANDING CARRIER AND ELEMENT SPECIFIC DYNAMICS IN ORGANOHALIDE PEROVSKITE BY TL02 2:03 – 2:18 FEMTOSECOND TABLETOP XUV SPECTROSCOPY, Aastha Sharma, Max A Verkamp, Josh Vura-Weis STRONG FIELD COHERENCE BREAKING AS A TOOL FOR IDENTIFYING ROTATIONAL TRANSITIONS DUE TO TK03 2:21 – 2:36 METHYL ROTOR STATES: 2-HEXANONE, Sean Fritz, Piyush Mishra, Timothy S. Zwier MOS DIRECT DETERMINATION OF BAND GAP RENORMALIZATION IN PHOTO-EXCITED MONOLAYER 2, TL03 2:21 – 2:36 Fang Liu, Mark E Ziffer, Kameron R Hansen, Jue Wang, Xiaoyang Zhu DETECTION OF TRACE AMOUNT OF WATER IN VOLATILE ORGANIC COMPOUNDS BY A K-BAND MOLEC- TK04 2:39 – 2:54 ULAR ROTATIONAL RESONANCE SPECTROSCOPY , Sandeep C Singh, Sylvestre Twagirayezu, Matt Muckle, Alex RAPID HOLE COOLING AND SLOW ELECTRON COOLING IN METHYLAMMONIUM LEAD IODIDE PER- Mikhonin, Justin L. Neill OVSKITE, Max A Verkamp, Aastha Sharma, Josh Vura-Weis TL04 2:39 – 2:54 Intermission COMPARATIVE STUDIES OF PHOTO PHYSICAL PROPERTIES OF SOME COUMARINS : SOLVENTS AND SUB- STITUENTS EFFECT., Sanjay Kumar TK05 3:33 – 3:48 ACHIEVING SURFACE SENSITIVITY IN ULTRAFAST XUV SPECTROSCOPY, Robert Baker, Somnath Biswas, Jakub TL05 2:57 – 3:12 Husek, Stephen Londo SPECTROSCOPIC TREASURE IN FORGOTTEN DATA: ROTATIONAL SPECTRUM ANALYSIS THROUGH AGGRE- GATED DATABASES, Matt Muckle, Justin L. Neill, Dave McDaniel, Alex Mikhonin TK06 3:51 – 4:06 CHARGE CARRIER DYNAMICS OF ANATASE TiO2 PROBED BY EXTREME ULTRAVIOLET REFLECTION- TL06 3:15 – 3:30 ABSORPTION SPECTROSCOPY , Emily B Hruska, Jakub Husek, Robert Baker AUTOMATED, CONTEXT-FREE ASSIGNMENT OF ASYMMETRIC ROTOR MICROWAVE SPECTRA, Lia Yeh,Lin- coln Satterthwaite, David Patterson TK07 4:09 – 4:24 Intermission ELEMENT-SPECIFIC MEASUREMENT OF HOLE TRANSPORT IN A Ni-TiO2-Si PHOTOLECTRODE USING TRAN- SIENT EXTREME ULTRAVIOLET SPECTROSCOPY, Scott Kevin Cushing TL07 4:09 – 4:24 ROTATIONAL SPECTROSCOPY OF FLAVOR COMPOUNDS IN PEACH BRANDY FOR PROCESS MONITORING IN TK08 4:27 – 4:42 CRAFT DISTILLERIES, Channing West, Thomas Miller, Noah Khan-Rafii, Emily Plunkett, Alexander Chmielinski, John DIRECT OBSERVATION OF EXCITON DISSOCIATION AND CHARGE INJECTION: THE FIRST-STEP IN SOLAR Hurst, Thomas Delaney, Charles Preston, Brooks Pate, Justin L. Neill, Robin A. Felder ENERGY CONVERSION TECHNOLOGIES, Somnath Biswas, Jakub Husek, Stephen Londo, Elizabeth A Fugate, Robert TL08 4:27 – 4:42 Baker 3 + TIME-RESOLVED POPULATIONS OF N2(A Σ ,v) IN NANOSECOND PULSE DISCHARGE PLASMAS, TK09 4:45 – 5:00 u ULTRAFAST X-RAY MULTI-EDGE SPECTROSCOPY WITH 100kHz OPCPA-DRIVEN HIGH HARMONIC GENERA- Elijah R Jans, Kraig Frederickson, Terry A. Miller, Igor V. Adamovich TION SOURCE, Elio G Champenois, Amy Cordones-Hahn, James P Cryan, Thomas JA Wolf TL09 4:45 – 5:00 MACHINE LEARNING APPLIED TO RAMAN SPECTRA OF PANCREATIC CANCER CELLS TO IDENTIFY MOLEC- ULAR SIGNATURES, PATTERNS AND PROTEIN EXPRESSIONS., Christopher Mandrell, Sakineh E.M. Abadi, Farhan Chowdhury, P Sivakumar TL10 5:03 – 5:18 POPULATION ENHANCEMENT AND ROTATIONAL CHARACTERIZATION OF GAUCHE-ISOPRENE BY HIGH RESOLUTION FTMW SPECTROSCOPY, Jessie P Porterfield, J. H. Westerfield, Lincoln Satterthwaite, David Patterson, Bryan Changala, Joshua H Baraban, Michael C McCarthy 20 21 WA. Astronomy WB. Mini-symposium: Non-covalent Interactions Wednesday, June 19, 2019 – 8:30 AM Wednesday, June 19, 2019 – 8:30 AM Room: 116 Roger Adams Lab Room: 100 Noyes Laboratory Chair: Michael C McCarthy, Harvard-Smithsonian Ctr for Astrophysics, Cambridge, MA, USA Chair: Josh Newby, Hobart and William Smith Colleges, Geneva, NY, USA

WA01 8:30 – 8:45 WB01 INVITED TALK 8:30 – 9:00 FORMATION OF INTERSTELLAR C60 FROM SILICON CARBIDE CIRCUMSTELLAR GRAINS, Jacob Bernal,Lucy NON-COVALENT INTERACTIONS ON THE BRINK OF CHEMICAL CHANGE , Kenneth R. Leopold M. Ziurys, Pierre Haenecour, Jane Howe, Thomas J. Zega, Sachiko Amari WB02 9:06 – 9:21 WA02 8:48 – 9:03 THE CO–(D2O)2 AND CO–(D2O)3 COMPLEXES: INFRARED SPECTRA AND STRUCTURAL CALCULATIONS, A. TOWARDS A MECHANISM FOR FORMATION OF SILICON CARBIDE CRYSTALS IN AGB STARS, Jesse J Lutz, J. Barclay, Koorosh Esteki, Andrea Pietropolli Charmet, Bob McKellar, Nasser Moazzen-Ahmadi Xiaofeng F Duan, Larry W Burggraf WB03 9:24 – 9:39 WA03 9:06 – 9:21 THE COMPLICATED CONFORMATIONAL LANDSCAPES OF TETRAHYDRO-2-FUROIC DIMER AND MONO- 4 IDENTIFICATION OF VO (X Σ) IN THE ENVELOPE OF VY CMa: A NEW CIRCUMSTELLAR MOLECULE, HYDRATE: BROADBAND ROTATIONAL SPECTRA AND COMPREHENSIVE CONFORMATIONAL SEARCHES, Jacob Bernal, Lucy M. Ziurys, Roberta M. Humphreys Fan Xie, Nathan A. Seifert, Matthias Heger, Wolfgang Jager,¨ Yunjie Xu WA04 9:24 – 9:39 WB04 9:42 – 9:57 IDENTIFYING TITAN’S ATMOSPHERE – A LOOK AT HYDROCARBONS POTENTIALLY PRESENT IN THE AT- CONFORMATIONAL LANDSCAPE OF 3-MERCAPTOPROPIONIC ACID AND METHYL 3- MOSPHERE OF SATURN’S MOST INTERESTING MOON, Daniel M. Hewett, Andy Wong, Peter F. Bernath, Brant E. MERCAPTOPROPIONATE REVEALED BY MICROWAVE SPECTROSCOPY AND THEORETICAL CALCULATIONS, Billinghurst Weslley G. D. P. Silva, Jennifer van Wijngaarden Intermission WB05 10:00 – 10:15 WA05 10:18 – 10:33 ROTATIONAL SIGNATURES OF DISPERSIVE STACKING IN THE FORMATION OF AROMATIC DIMERS, MID-IR OBSERVATIONS OF THE LATE-TYPE STARS VY CMa AND o-CETI USING IRTF-TEXES AROUND 8 AND Mariyam Fatima, Amanda Steber, Anja Poblotzki, Cristobal Perez, Sabrina Zinn, Melanie Schnell 10μm, Guido W Fuchs, Daniel Witsch, Alexander A. Breier,ThomasGiesen Intermission WA06 10:36 – 10:51 WB06 10:54 – 11:09 THE TRANSITION FROM DIFFUSE ATOMIC GAS TO MOLECULAR CLOUD IN TAURUS, Steven Federman, COLD ION SPECTROSCOPY OF PYRIDINIUM IONS: AN EXPERIMENTAL PROBE TO EVALUATE NON- Johnathan S Rice, Adam Ritchey, Hwihyun Kim, John H. Lacy, Paul F Goldsmith, Nicolas Flagey, Gregory N. Mace, David COVALENT INTERACTIONS IN THE GAS PHASE, Alexandra Tsybizova, Vladimir Gorbachev, Larisa Miloglyadova, L. Lambert Peter Chen WA07 10:54 – 11:09 WB07 11:12 – 11:27 EXO-PLANETARY HIGH-TEMPERATURE HYDROCARBONS BY EMISSION AND ABSORPTION SPEC- MICROWAVE SPECTRUM OF A SUPERACID AND ITS MONOHYDRATE: TUNNELING AND LARGE AMPLITUDE TROSCOPY (e-PYTHEAS PROJECT), Vincent Boudon, Athena Coustenis, Alain Campargue, Robert Georges, Vladimir MOTION IN CF3SO2OH AND CF3SO2OH-H2O, Anna Huff, Nathan Love, CJ Smith, Kenneth R. Leopold Tyuterev WB08 11:30 – 11:45 WA08 11:12 – 11:27 LIF STUDY FOR THE VIBRONIC STRUCTURE OF PARA-FLUOROPHENOL...AMMONIA BINARY COMPLEX , ABSORPTION CROSS SECTIONS OF ISOBUTANE AND ITS POTENTIAL PRESENCE IN TITAN’S ATMOSPHERE, Souvick Biswas, Tapas Chakraborty Daniel M. Hewett, Dror M. Bittner, Andy Wong, Peter F. Bernath, Brant E. Billinghurst, Jianbao Zhao, Nicholas Lombardo, Conor A Nixon, Don Jennings WB09 11:48 – 12:03 FLUORESCENCE DYNAMICS OF EXCITED STATE PROTON TRANSFER IN SALICYLIC ACID: REVISITED, Hirdyesh Mishra WB10 12:06 – 12:21 EFFECT OF UREA ON WATER HYDROGEN-BOND NETWORK AND DENATURATION OF PROTEIN. , Sneha Banerjee, Sohini Sarkar, Rapti Goswami, Pankaj Mandal 22 23 WC. Instrument/Technique Demonstration WD. Electronic structure, potential energy surfaces Wednesday, June 19, 2019 – 8:30 AM Wednesday, June 19, 2019 – 8:30 AM Room: 1024 Chemistry Annex Room: 217 Noyes Laboratory Chair: Brooks Pate, The University of Virginia, Charlottesville, VA, USA Chair: Michael Heaven, Emory University, Atlanta, GA, USA

WC01 8:30 – 8:45 WD01 8:30 – 8:45 A NEW E-BAND CHIRPED PULSE SPECTROMETER FOR CHEMICAL KINETICS APPLICATIONS, Brian M Hays, LASER-INDUCED FLUORESCENCE (LIF) OF JET-COOLED THORIUM NITRIDE (ThN), Joel R Schmitz, Michael Theo Guillaume, Thomas Sandow Hearne, Omar Abdelkader Khedaoui, Ilsa Rose Cooke, Divita Gupta, Sebastien D. Le Heaven Picard, Robert Georges, Abdessamad Benidar, Ludovic Biennier, Ian R. Sims WD02 8:48 – 9:03 WC02 8:48 – 9:03 EXPERIMENTAL DETERMINATION OF THE POTENTIAL ENERGY FUNCTION OF THE COPPER DIMER PERFORMANCE OF A 6-18 GHZ DDS-BASED SEGMENTED CHIRP PULSE FOURIER TRANSFORM MICROWAVE GROUND STATE, Peter Bornhauser, Martin Beck, Qiang Zhang, Gregor Knopp, Roberto Marquardt, Peter Radi SPECTROMETER, Haley N. Scolati, Anna L Pischer, Kelly S. Meyer, J. H. Westerfield, Kyle N. Crabtree WD03 9:06 – 9:21 FITTING AN ACCURATE AB INITIO POTENTIAL ENERGY SURFACE FOR THE GROUND ELECTRONIC STATE OF WC03 9:06 – 9:21 16 −1 HORNLESS CHIRPED PULSE FOURIER TRANSFORM MICROWAVE SPECTROMETER, Emily Dunkel, Chris Dew- H2 O INCLUDING ENERGY LEVELS UP TO 37 000 cm , Eamon K Conway, Iouli E Gordon, Aleksandra A. Kyuberis, berry Oleg L. Polyansky, Sergei N. Yurchenko, Nikolay F. Zobov WC04 9:24 – 9:39 WD04 9:24 – 9:39 DIRECT INSITU MEASUREMENTS OF ABSOLUTE CARRIER ENVELOPE PHASE OF ULTRASHORT PULSES, AB INITIO STUDY OF GROUND-STATE CS PHOTODISSOCIATION VIA HIGHLY EXCITED ELECTRONIC STATES, Duke A. Debrah, Gihan Basnayake, Gabriel A. Stewart, Wen Li Zhongxing Xu, Nan Luo, William M. Jackson, Cheuk-Yiu Ng, Steven Federman, Lee-Ping Wang, Kyle N. Crabtree WC05 9:42 – 9:57 WD05 9:42 – 9:57 MULTI-ANTENNAE DETECTION IN A CP-FTMW SPECTROMETER, Frank E Marshall, Amanda Jo Duerden, Nicole EVALUATING VPT2 SCHEMES FOR ACCURATE AUTOMATED THERMOCHEMISTRY AND SPECTROSCOPY Moon, Kristen Donnell, G. S. Grubbs II FOR NON-COVALENT SYSTEMS , Bradley Welch, Richard Dawes, Ernesto Quintas Sanchez,´ Branko Ruscic, David H. WC06 10:00 – 10:15 Bross 3D PRINTED ANTENNA DESIGNS FOR FOURIER TRANSFORM MICROWAVE SPECTROSCOPY, John K Kopp,Nick Intermission Knowles, Chris Dewberry WD06 10:36 – 10:51 Intermission ELECTRON IMPACT EXCITATION OF GAS-PHASE GUANINE MOLECULES, I.I. Shafranyosh, Yu.Yu. Svyda, M.I. Sukhoviya, M.I. Shafranyosh WC07 10:54 – 11:09 A 180 GHZ PULSED TRANSMITTER AND HETERODYNE RECEIVER 28 NM CMOS CHIPSET FOR MOLECULAR WD07 10:54 – 11:09 SENSING, Deacon J Nemchick, Brian Drouin, Adrian Tang, Maria Alonso, Yanghyo Kim, M.-C. Frank Chang ELECTRONIC AND VIBRATIONAL STRUCTURE OF BUCKY BOWL, Masaaki Baba, Ayumi Kanaoka, Masatoshi Mis- WC08 11:12 – 11:27 ono, Hidehiro Sakurai, Masashi Tsuge, Pavithraa Sundararajan, Yuan-Pern Lee A LOW-BUDGET, RESEARCH GRADE, BALLE-FLYGARE CAVITY FTMW SPECTROMETER IMPLEMENTED FOR WD08 11:12 – 11:27 THE TEACHING LABORATORY, Amanda Jo Duerden, Nicole Moon, G. S. Grubbs II HIGH-RESOLUTION LASER SPECTROSCOPY OF THE S1 ← S0 TRANSITION OF FLUORENE AND CARBAZOLE, WC09 11:30 – 11:45 Shunji Kasahara, Shinji Kuroda, Shoya Ueda ROTATIONAL SPECTROSCOPY: A LABORATORY FOR UNDERGRADUATE PHYSICAL CHEMISTRY, Nicole Moon, WD09 11:30 – 11:45 Amanda Jo Duerden, G. S. Grubbs II LIF SPECTROSCOPY OF LINEAR SiOSi, Masaru Fukushima, Takashi Ishiwata WC10 11:48 – 12:03 WD10 Post-Deadline Abstract 11:48 – 12:03 TWO-DIMENSIONAL LASER INDUCED FLUORESCENCE SPECTROSCOPY OF MGOMG, Sean Michael Bresler, THE ELECTRONIC STRUCTURE OF THE PLANARIZED BLATTER RADICAL AND ITS DERIVATIVES., Joel R Schmitz, Michael Heaven Aniket Hande, Clovis Darrigan, Piotr Kaszynski,´ Anna Chrostowska 24 25 WE. Mini-symposium: High-Harmonic Generation and XUV Spectroscopy WF. Ions Wednesday, June 19, 2019 – 8:30 AM Wednesday, June 19, 2019 – 8:30 AM Room: B102 Chemical and Life Sciences Room: 2079 Natural History Chair: Agnieszka Jaron-Becker, University of Colorado, Boulder, USA Chair: Gary E. Douberly, The University of Georgia, Athens, GA, USA

WE01 Journal of Molecular Spectroscopy Review Lecture 8:30 – 9:00 WF01 8:30 – 8:45 + SIMULATING STRONG FIELD RESCATTERING USING ATTOSECOND LIGHT, Louis DiMauro HIGHLY-ACCURATE EXPERIMENTALLY DETERMINED ENERGY LEVELS OF H3 , Charles R. Markus,BenjaminJ. WE02 9:06 – 9:21 McCall CHARACTERIZATION OF PHOTOINDUCED VALENCE TAUTOMERISM IN A COBALT DIOXOLENE COMPLEX WF02 8:48 – 9:03 BY FEMTOSECOND M-EDGE SPECTROSCOPY, Ryan T Ash, Kaili Zhang, Josh Vura-Weis PURE ROTATIONAL SPECTRUM OF CN+, Sven Thorwirth, Phillip Schreier, Thomas Salomon, Stephan Schlemmer, Os- kar Asvany WE03 9:24 – 9:39 DETERMINING THE PRESENCE OF SPIN DYNAMICS IN COBALT FERRITE THIN FILMS USING XUV-RA SPEC- WF03 9:06 – 9:21 − TROSCOPY, Stephen Londo, Somnath Biswas, Jakub Husek, Robert Baker AUTODETACHMENT OF CH2CN VIEWED WITH HIGH RESOLUTION PHOTOELECTRON IMAGING, Benjamin A Laws, Stephen T Gibson, Richard Mabbs WE04 9:42 – 9:57 OBSERVATION OF TRANSIENT HIGH-VALENT STATES IN THE WATER OXIDATION CATALYST CoIII4O4 WF04 9:24 – 9:39 + + CUBANE VIA EXTREME ULTRAVIOLET SPECTROSCOPY, Yusef A. Shari’ati, Josh Vura-Weis SPECTROSCOPIC STUDIES OF PROTONATED AMINES: CH3NH3 AND C2H5NH3 , Sven Thorwirth, Philipp C Intermission Schmid, Matthias Topfer,¨ Sandra Brunken,¨ Oskar Asvany, Stephan Schlemmer WE05 10:36 – 10:51 WF05 9:42 – 9:57 CALCULATIONS OF MICROSCOPIC AND MACROSCOPIC PROPERTIES OF HIGH-HARMONIC GENERATION HINDERING AN ION-NEUTRAL REACTION USING VIBRATIONAL EXCITATION: THE ν7 ROVIBRATIONAL + FROM MOLECULAR IONS, T Joyce, Agnieszka Jaron-Becker BAND OF c-C3H2 , Charles R. Markus, Oskar Asvany, Thomas Salomon, Philipp C Schmid, Shreyak Banhatti, Filippo Lipparini, Jurgen¨ Gauss, Sandra Brunken,¨ Stephan Schlemmer WE06 10:54 – 11:09 APPLYING XUV SPECTROSCOPY TO OBSERVE SPIN-ORBIT STATE DEPENDENCE ON STRONG-FIELD IONIZA- Intermission TION, Scott G Sayres WF06 10:36 – 10:51 INFRARED PHOTODISSOCIATION SPECTROSCOPY AND MULTIREFERENCE ANHARMONIC VIBRATIONAL WE07 11:12 – 11:27 HO+ ATTOSECOND STREAKING TIME DELAYS: FINITE-RANGE INTERPRETATION AND APPLICATIONS, STUDY OF THE 4 MOLECULAR CATION, Peter R. Franke, Michael A Duncan, Gary E. Douberly Andreas Becker, Cory Goldsmith, T Joyce, Agnieszka Jaron-Becker WF07 10:54 – 11:09 − WE08 11:30 – 11:45 AUTODETACHMENT AND VIBRONIC COUPLED PHOTODETACHMENT TRANSITIONS OF C2H3O , GENERATION AND STUDY OF FEW-FEMTOSECOND VIBRATIONAL WAVE-PACKETS VIA STRONG-FIELD ION- Stephen T Gibson,BenjaminALaws IZATION, Lauren F Heald, Scott G Sayres WF08 11:12 – 11:27 VELOCITY MAP IMAGING OF DISSOCIATIVE CHARGE TRANSFER IN TRANSITION METAL ION - MOLECULE COMPLEXES, Brandon M. Rittgers, Daniel Leicht, Michael A Duncan WF09 11:30 – 11:45 THRESHOLD IONIZATION SPECTROSCOPY AND SPIN-ORBIT COUPLING OF CeC3H4 and CeC3H6 FORMED in Ce + PROPENE REACTION, Yuchen Zhang, Wenjin Cao, Dong-Sheng Yang WF10 11:48 – 12:03 SOLVATOCHROMIC BEHAVIOR OF THE ANIONIC BIOCHROMOPHORE BILIVERDIN INVESTIGATED USING A CRYOGENIC ION TRAP, Wyatt Zagorec-Marks, Leah G Dodson, J. Mathias Weber 26 27 WG. Mini-symposium: Astrochemistry and Astrobiology in the age of ALMA WH. Mini-symposium: Non-covalent Interactions Wednesday, June 19, 2019 – 1:45 PM Wednesday, June 19, 2019 – 1:45 PM Room: 116 Roger Adams Lab Room: 100 Noyes Laboratory Chair: Eric R. Willis, The University of Virginia, Charlottesville, VA, USA Chair: Mar´ıa Mar Quesada-Moreno, Deutsches Elektronen-Synchrotron, Hamburg, Germany

WG01 INVITED TALK 1:45 – 2:15 WH01 1:45 – 2:00 ASTROCHEMISTRY OF STAR FORMING REGIONS: FROM SINGLE DISH TO INTERFEROMETRIC OBSERVA- JET-COOLED HIGH RESOLUTION INFRARED LASER SPECTROSCOPY OF Kr-H2O IN THE REGION OF THE TIONS, Charlotte Vastel BENDING MODE OF H2O , Yacine Belkhodja, Pierre Asselin, Yann Berger WG02 2:21 – 2:36 + WH02 2:03 – 2:18 DETECTION OF CCCH TOWARD W49N: ELUCIDATING THE MOLECULAR COMPLEXITY OF THE DIFFUSE THE WATER–CARBON MONOXIDE DIMER: NEW INFRARED SPECTRA, AB INITIO ENERGY LEVEL CAL- INTERSTELLAR GAS, Harshal Gupta, Kelvin Lee, Michael C McCarthy CULATIONS, AND A CURIOUS INTERMOLECULAR MODE, A. J. Barclay, Koorosh Esteki, Bob McKellar, Nasser Moazzen-Ahmadi WG03 2:39 – 2:54 AN ALMA SUB-ARCSECOND VIEW OF MOLECULAR GAS IN MASSIVE STAR-FORMING REGION G10.6-0.4, WH03 2:21 – 2:36 Charles John Law, Qizhou Zhang, Karin I Oberg,¨ Roberto Galvan-Madrid,´ Eric Keto, Paul T. P. Ho, Hauyu Baobab Liu INTERNAL ROTATION OF INTRAMOLECULAR HYDROGEN BONDING OF OH OR NH2 GROUPS ATTACHED TO THREE-MEMBERED RING MOLECULES, Esther Juliana Ocola, Jaan Laane WG04 2:57 – 3:12 CONSTRAINING COSMIC-RAY IONIZATION RATES AND CHEMICAL TIMESCALES IN MASSIVE HOT CORES , WH04 2:39 – 2:54 Christopher J Barger, Robin T. Garrod INFRARED BANDS OF CS2 DIMER AND TRIMER AT 4.5 μm, A. J. Barclay, Koorosh Esteki, K. H. Michaelian, Bob McKellar, Nasser Moazzen-Ahmadi WG05 3:15 – 3:30 INTERSTELLAR GLYCOLALDEHYDE, METHYL FORMATE, AND ACETIC ACID: BI-MODAL ABUNDANCE PAT- WH05 2:57 – 3:12 TERNS IN STAR-FORMING REGIONS, Samer El-Abd, Crystal L. Brogan, Todd R. Hunter, Eric R. Willis, Robin T. Garrod, IN SITU STUDIES OF ELECTROCHEMICAL REACTIONS USING VIBRATIONAL SUM FREQUENCY GENERA- Brett A. McGuire TION, Spencer Wallentine, Savini Sandunika Bandaranayake, Robert Baker Intermission Intermission WG06 4:09 – 4:24 WH06 3:51 – 4:06 PURE ROTATIONAL STUDY OF CYANOPHENYLACETYLENE (C6H5C3N), Zachary Buchanan, Olivia Chitarra, Kelvin THEMOSTSTABLEISOMEROFC4H2-(OCS)2 VAN DER WAALS COMPLEX: THEORY AND EXPERIMENT CON- Lee, Michael C McCarthy, Olivier Pirali, Marie-Aline Martin-Drumel FIRM A STRUCTURE WITH C2 SYMMETRY, A. J. Barclay, Andrea Pietropolli Charmet, Bob McKellar, Nasser Moazzen- WG07 4:27 – 4:42 Ahmadi SEARCHING FOR A NITROGEN-HETEROCYCLE PRECURSOR: THE ROTATIONAL SPECTRUM OF THE β- WH07 4:09 – 4:24 CYANOVINYL RADICAL, Sommer L. Johansen, Marie-Aline Martin-Drumel, Kyle N. Crabtree LASER SPECTROSCOPY OF OCS-WATER COMPLEXES IN SUPERFLUID HELIUM NANODROPLETS, Isaac James Miller, Tyler Wells, Ty Faulkner, Paul Raston WG08 4:45 – 5:00 GOTHAM AND ARKHAM: FIRST RESULTS FROM PROGRAMS TO EXPLORE AROMATIC CHEMISTRY AT THE WH08 4:27 – 4:42 EARLIEST STAGES OF STAR FORMATION , Brett A. McGuire, Andrew M Burkhardt, Kelvin Lee, Ryan Loomis, Steven CHARACTERIZATION OF A HYDROGEN PEROXIDE-BENZENE COMPLEX USING MATRIX ISOLATION IN- B Charnley, Martin Cordiner, Eric Herbst, Sergei Kalenskii, Christopher N Shingledecker, Eric R. Willis, Ci Xue, Anthony FRARED SPECTROSCOPY, Jay C. Amicangelo, Dylan Johnson, Catherine Kaiser, Yudhishtara Payagala, Jacob Oslosky, Remijan, Michael C McCarthy Lia Totleben WG09 5:03 – 5:18 WH09 4:45 – 5:00 MILLIMETER-WAVE SPECTROSCOPY OF FLEXIBLE ORGANIC MOLECULES AND COMPARISON WITH AS- WEAKLY-BOUND COMPLEXES OF THIOPHENE AND WATER AS INVESTIGATED BY MATRIX ISOLATION FTIR TRONOMICAL SURVEYS, Sonia Melandri, Assimo Maris, Luca Evangelisti, Imanol Usabiaga, Camilla Calabrese, Laura AND COMPUTATION , Joshua G Wasserman, Keshihito J Murphy, Josh Newby B. Favero WH10 5:03 – 5:18 INFRARED PHOTODISSOCIATION SPECTROSCOPY OF PROTONATED AMMONIA CLUSTERS IN THE GAS PHASE, Jason E. Colley, J. Philipp Wagner, Michael A Duncan 28 29 WI. Structure determination WJ. Metal containing Wednesday, June 19, 2019 – 1:45 PM Wednesday, June 19, 2019 – 1:45 PM Room: 1024 Chemistry Annex Room: 217 Noyes Laboratory Chair: M. Eugenia Sanz, King’s College London, London, United Kingdom Chair: Caroline Chick Jarrold, Indiana University, Bloomington, IN, USA

WI01 1:45 – 2:00 WJ01 1:45 – 2:00 IDENTIFYING THE DIFFERENCES IN CONJUGATED VS. NON-CONJUGATED BIOMOLECULES IN CANCER RE- MASS-INDEPENDENT DUNHAM ANALYSIS OF THE KNOWN ELECTRONIC STATES OF PtS, Jack C Harms,Leah SEARCH USING VIBRATIONAL SPECTROSCOPY, Robinson Karunanithy, Torrey E. Holland, P Sivakumar C O’Brien, James J O’Brien WI02 2:03 – 2:18 WJ02 2:03 – 2:18 CONFORMATION-SPECIFIC IR AND UV SPECTROSCOPY OF A SERIES OF SYNTHETIC FOLDAMERS: α/β3- MASS-INDEPENDENT DUNHAM ANALYSIS OF NEW ELECTRONIC TRANSITIONS OF PtX (X=F, Cl) OBSERVED AND β3- ALA DIPEPTIDES , Dewei Sun, Karl N. Blodgett, Joshua L. Fischer, Timothy S. Zwier USING INTRACAVITY LASER SPECTROSCOPY, Jack C Harms,LeahCO’Brien,JamesJO’Brien WJ03 2:21 – 2:36 WI03 2:21 – 2:36 + FOURIER TRANSFORM MICROWAVE SPECTRUM OF CIS-3-HEXENAL, Seiya Yoshizawa, Nobuhiko Kuze, Yoshiyuki EXAMINING THE LOW ENERGY STATES OF NDO USING TWO-PHOTON IONIZATION , Thomas D. Persinger, Kawashima Robert A. VanGundy, Michael Heaven WI04 2:39 – 2:54 WJ04 2:39 – 2:54 CONFORMATIONAL ANALYSIS OF γ-HEXANOLACTONE BY MICROWAVE SPECTROSCOPY, Takahiro Takimoto, IDENTIFICATION OF TWO NEW ELECTRONIC TRANSITIONS OF TaF USING INTRACAVITY LASER SPEC- Nobuhiko Kuze, Yoshiyuki Kawashima TROSCOPY, Kristin N Bales, Jack C Harms, Leah C O’Brien, James J O’Brien WI05 2:57 – 3:12 Intermission FOURIER TRANSFORM MICROWAVE SPECTRA OF 1-PENTANETHIOL, Kojiro Suzuki, Nobuhiko Kuze, Yoshiyuki WJ05 3:33 – 3:48 Kawashima IDENTIFICATION OF THE FIRST ROTATIONALLY RESOLVED ELECTRONIC TRANSITIONS OF TUNGSTEN SUL- WI06 3:15 – 3:30 FIDE OBSERVED USING INTRACAVITY LASER SPECTROSCOPY, Kristin N Bales, Jack C Harms, Leah C O’Brien, BROADBAND MICROWAVE SPECTROSCOPY OF TRANS 3-PENTENENITRILE AND ITS PYROLYSIS PRODUCTS, James J O’Brien Piyush Mishra, Sean Fritz, Brian M Hays, Timothy S. Zwier WJ06 3:51 – 4:06 PHOTOELECTRON VELOCITY MAP IMAGING SPECTROSCOPY OF BERYLLIUM-CONTAINING TRIATOMIC Intermission − ANIONS, BeX2 (X=O,C), Mallory Theis, Noah B Jaffe, Michael Heaven WI07 4:09 – 4:24 AN INVESTIGATION OF THE NUCLEAR QUADRUPOLE COUPLING TENSORS OF 2-BROMOPYRIDINE USING WJ07 4:09 – 4:24 1 THE EXTENDED TOWNES-DAILEY ANALYSIS, Angela Y. Chung, Eric A. Arsenault, Susanna L. Stephens, Wallace C. FOURIER TRANSFORM MICROWAVE SPECTROSCOPY OF LiNH2 and NaNH2 (X˜ A1): COMPARING Pringle, Carlos A Jimenez-Hoyos, S. A. Cooke, Stewart E. Novick QUADRUPOLE HYPERFINE INTERACTIONS, Mark Burton, Benjamin Russ, Phillip M. Sheridan, Lucy M. Ziurys WI08 4:27 – 4:42 WJ08 4:27 – 4:42 CONCERNING THE GROUND STATE STRUCTURES OF TWO PARTIALLY FLUORINATED CYCLOPENTANES THE 3d BROMIDE SERIES: THE PURE ROTATIONAL SPECTRUM OF CrBr (X6Σ+),TylerJHerman,LucyM.Ziurys C5H3F7 AND C5H2F8,A.J.Minei,S.A.Cooke WJ09 4:45 – 5:00 WI09 4:45 – 5:00 FTIR STUDY OF THE REACTIVITY OF TITANIUM ATOMS WITH CARBON MONOXIE AND WATER ISOLATED STRUCTURAL DETERMINATION OF THE CHIRAL MOLECULE 2-BROMO-1,1,1,3-TETRAFLUOROETHANE BY IN SOLID ARGON, Mohamad Ibrahim, Pascale Soulard, Esma¨ıl Alikhani, Benoˆıt Tremblay CP-FTMW SPECTROSCOPY, Joshua E. Isert, Frank E Marshall, G. S. Grubbs II WJ10 5:03 – 5:18 WI10 5:03 – 5:18 MATI SPECTROSCOPY OF Ln(OH)2 (Ln = La AND Ce) FORMED BY O-H BOND ACTIVATION OF WATER., THE FEASIBILITY OF DETERMINING THE CARBON FRAMEWORK GEOMETRY OF A MOLECULE FROM Silver Nyambo, Jong Hyun Kim, Priya Karna, Yuchen Zhang, Dong-Sheng Yang ANALYSIS OF THE CARBON-13 ISOTOPOLOGUE ROTATIONAL SPECTRA IN NATURAL ABUNDANCE, Kevin J Mayer, Brooks Pate, Eleanor Patrinely, Emmit Pert, Austin Cheng, Kira Baugh, Kevyn Hadley, Sean Lee, George Fairman, Jake Butler, Gaetan Banawoe, Ignacio Simon 30 31 WK. Mini-symposium: High-Harmonic Generation and XUV Spectroscopy WL. Spectroscopy as an analytical tool Wednesday, June 19, 2019 – 1:45 PM Wednesday, June 19, 2019 – 1:45 PM Room: B102 Chemical and Life Sciences Room: 2079 Natural History Chair: Robert Baker, The Ohio State University, Columbus, OH, USA Chair: Jessie P Porterfield, Harvard Smithsonian Ctr for Astrophysics, Cambridge, MA, USA

WK01 INVITED TALK 1:45 – 2:15 WL01 1:45 – 2:00 ULTRAFAST XUV SPECTROSCOPY TO PROBE CONICAL INTERSECTIONS AND EXCITED STATE DYNAMICS, DETERMINATION OF ENANTIOMERIC EXCESS IN THE HIGH ENANTIOPURITY LIMIT USING CHIRAL TAG- Arvinder Sandhu GING ROTATIONAL SPECTROSCOPY, Kevin J Mayer, Brooks Pate, Channing West, Reilly E. Sonstrom, Martin S. Hol- WK02 2:21 – 2:36 dren, Taylor Smart, Luca Evangelisti THE ELECTRONIC PROPERTIES OF 2D-TaS2 BASED PHOTOCATALYTIC MATERIALS INVESTIGATED BY FS- WL02 2:03 – 2:18 XUV PHOTOEMISSION SPECTROSCOPY, Mihai E Vaida CALIBRATING THE ENANTIOMERIC EXCESS OF CHIRAL TAGS TO IMPROVE MEASUREMENT ACCURACY WK03 2:39 – 2:54 USING A SIMPLIFIED 6-18 GHZ CHIRPED-PULSE FOURIER TRANSFORM MICROWAVE SPECTROMETER, THE ROLE OF LATTICE DEFECTS ON THE ELECTRON DYNAMICS AND PHOTOCHEMISTRY OF CuFeO2 DE- Channing West, Luca Evangelisti, Reilly E. Sonstrom, Brooks Pate LAFOSSITE, Elizabeth A Fugate, Somnath Biswas, Yutichai Mueanngern, Mathew Clement, Minkyu Kim, Dongjoon Kim, WL03 2:21 – 2:36 Aravind Asthagiri, Robert Baker QUANTITATIVE DETERMINATION OF ENANTIOMERIC EXCESS BY MICROWAVE THREE-WAVE MIXING, WK04 2:57 – 3:12 Martin S. Holdren, Brooks Pate, Taylor Smart, Arthur Wu TOWARDS EXTREME ULTRAVIOLET TIME-RESOLVED LIQUID PHOTOELECTRON SPECTROSCOPY UTILIZ- WL04 2:39 – 2:54 ING A HIGH-HARMONIC GENERATION PROBE SOURCE, Zachary N. Heim, Blake A Erickson, Erica Liu, Daniel PERFORMANCE OF THREE-WAVE MIXING ROTATIONAL SPECTROSCOPY FOR THE DETERMINATION OF Neumark ENANTIOMERIC EXCESS IN COMPLEX CHEMICAL MIXTURES, Taylor Smart, Brooks Pate, Martin S. Holdren, Intermission Arthur Wu WK05 3:51 – 4:06 Intermission DEVELOPMENT OF SOLUTION-PHASE XUV ABSORPTION SPECTROSCOPY, Kori Sye, Josh Vura-Weis WL05 3:33 – 3:48 WK06 4:09 – 4:24 CHIRAL ANALYSIS OF THUJONE IN ESSENTIAL OIL SAMPLES, Reilly E. Sonstrom, Kevin J Mayer, Channing West, CONTROLLING PHOTOEXCITED STATE DYNAMICS AT HEMATITE SURFACES, Savini Sandunika Bandaranayake, Brooks Pate Somnath Biswas, Robert Baker, Spencer Wallentine WL06 3:51 – 4:06 WK07 4:27 – 4:42 MOLECULAR SIZE LIMITS FOR ROTATIONAL SPECTROSCOPY AND THE HIGH-J LIMIT OF THE RIGID ROTOR, USING FEMTOSECOND TABLETOP XUV SPECTROSCOPY TO STUDY NICKEL CATALYSIS, Kristopher Benke, Brooks Pate, Luca Evangelisti, Justin L. Neill, Channing West Josh Vura-Weis WL07 4:09 – 4:24 PROGRESS ON THE DEVELOPMENT OF A MILLIMETER-WAVE CHIRALITY SPECTROMETER (CHIRALSPEC), Martin S. Holdren, Deacon J Nemchick, John Pearson, Shanshan Yu, Brooks Pate WL08 4:27 – 4:42 STEREOCHEMICAL IDENTIFICATION OF AN INTERMEDIATE IN THE SYNTHESIS OF DOLUTEGRAVIR USING MOLECULAR ROTATIONAL RESONANCE SPECTROSCOPY, Justin L. Neill, Matt Muckle, Luca Evangelisti, Reilly E. Sonstrom, Brooks Pate, Jo-Ann Jee, B Frank Gupton, Thomas D. Roper WL09 4:45 – 5:00 TERAHERTZ ANALYTICAL CHEMICAL SENSING OF EXPIRED HUMAN BREATH. , Daniel J Tyree, Hannah N Benston, Parker K Huntington, Brent D Foy, Ivan Medvedev WL10 5:03 – 5:18 TERAHERTZ SPECTROSCOPIC MOLECULAR SENSOR FOR QUANTITATIVE ANALYTICAL GAS SENSING, Daniel J Tyree, Parker K Huntington, Robert M Schueler, Jennifer Holt, Christopher F. Neese, Ivan Medvedev 32 33 RA. Plenary RG. Mini-symposium: Astrochemistry and Astrobiology in the age of ALMA Thursday, June 20, 2019 – 8:30 AM Thursday, June 20, 2019 – 1:45 PM Room: Foellinger Auditorium Room: 116 Roger Adams Lab Chair: Anthony Remijan, NRAO, Charlottesville, VA, USA Chair: Amanda Steber, Universitat¨ Hamburg, Hamburg, Germany

RA01 8:30 – 9:10 RG01 INVITED TALK 1:45 – 2:15 CURRENT AND FUTURE PROSPECTS, AS WELL AS CHALLENGES FOR ALMA MOLECULAR LINE STUDIES, TOWARD UNDERSTANDING CHEMICAL EVOLUTION ALONG PROTOPLANETARY DISK FORMATION, Crystal L. Brogan Nami Sakai RA02 9:15 – 9:55 RG02 2:21 – 2:36 MOLECULAR SPECTROSCOPY AT THE JET PROPULSION LABORATORY, Brian Drouin DUST POLARIZATION IN PROTOPLANETARY DISKS: EVIDENCE FOR MULTIPLE MECHANISMS AT WORK, Intermission Rachel E. Harrison, Leslie Looney, Ian Stephens, Zhi-Yun Li, Haifeng Yang, Akimasa Kataoka, Robert J Harris, Woojin Kwon, Takayuki Muto, Munetake Momose RAO AWARDS 10:35 RG03 2:39 – 2:54 Presentation of Awards by Jennifer van Wijngaarden, University of Manitoba THE DEVELOPMENT OF A SUBMILLIMETER SPECTROSCOPIC METHOD FOR DETECTING PHOTODESORBED ICES, Katarina Yocum, Ayanna Jones, Ethan Todd, Susanna L. Widicus Weaver, Stefanie N Milam 2018 Rao Award Winners Zaijun Chen, Max Planck Institute of Quantum Optics RG04 2:57 – 3:12 LASER ABLATION OF SOLID ORGANIC PRECURSORS AS AN ALTERNATIVE TOOL IN THE GENERATION OF Elijah Jans, The Ohio State University INTERSTELLAR MOLECULES, Lucie Kolesnikova´,IkerLeon,´ Elena R. Alonso, Santiago Mata, Jose´ L. Alonso Elizabeth Ryland, University of Illinois at Urbana-Champaign Intermission RG05 3:51 – 4:06 MILLER PRIZE 10:45 CONSTRAINING THE FORMATION OF FUNDAMENTAL INTERSTELLAR MOLECULES USING ISOTOPO- Introduction by Michael Heaven, Emory University LOGUES, Olivia H. Wilkins, Brandon Carroll, Geoffrey Blake RG06 4:09 – 4:24 26 RA03 Miller Prize Lecture 10:50 – 11:05 FIRST DETECTION OF THE RADIOACTIVE MOLECULE AlF AND ITS SPECTROSCOPIC ASPECTS, THE SUBTLE INTERACTIONS BETWEEN POLYCYCLIC AROMATIC HYDROCARBONS AND OTHER ASTRO- Alexander A. Breier, Guido W Fuchs, Thomas Giesen, Jurgen¨ Gauss, Tomasz Kaminski CHEMICALLY RELEVANT MOLECULES, Amanda Steber, Cristobal Perez, Sebastien´ Gruet, Donatella Loru, Berhane RG07 4:27 – 4:42 Temelso, George C Shields, Melanie Schnell INVESTIGATING ISOMERS OF ASTROPHYSICAL MOLECULES BY ROTATIONAL SPECTROSCOPY: THE CASE OF [C2H2O] COMPOUNDS, Marie-Aline Martin-Drumel, Kelvin Lee, Olivier Pirali, J.-C. Guillemin, Michael C McCarthy COBLENTZ AWARD 11:10 RG08 4:45 – 5:00 Presentation of Award by Linda Kidder-Yarlott, Coblentz Society SUBMILLIMETER WAVE SPECTROSCOPY AND ISM SEARCH FOR PROPIONIC ACID, L. Margules` ,R.A. Motiyenko, V. Ilyushin, Olga Dorovskaya, E. A. Alekseev, Elena R. Alonso, Lucie Kolesnikova,´ Jose Cernicharo, J.-C. Guillemin RA04 Coblentz Society Award Lecture 11:15 – 11:55 RG09 5:03 – 5:18 OPTICAL FREQUENCY COMB FOURIER TRANSFORM SPECTROSCOPY, Aleksandra Foltynowicz GLOBAL ANALYSIS OF THE NH2 RADICAL ROTATIONAL, VIBRATIONAL AND ELECTRONIC TRANSITIONS, Marie-Aline Martin-Drumel, Olivier Pirali, L. H. Coudert 34 35 RH. Mini-symposium: Non-covalent Interactions RI. Rotational structure/frequencies Thursday, June 20, 2019 – 1:45 PM Thursday, June 20, 2019 – 1:45 PM Room: 100 Noyes Laboratory Room: 1024 Chemistry Annex Chair: Rebecca A. Peebles, Eastern Illinois University, Charleston, IL, USA Chair: Kenneth R. Leopold, University of Minnesota, Minneapolis, MN, USA

RH01 1:45 – 2:00 RI01 1:45 – 2:00 THE STYRENE OXIDE DIMER STORY, Sergio R Domingos, Melanie Schnell BENZENE’S INFERNO. PART I: A MICROWAVE SPECTROSCOPIC INVESTIGATION, Michael C McCarthy,Kelvin Lee RH02 2:03 – 2:18 THE CONVERSION OF STYRENE OXIDE ENANTIOMERS INTO SPECTROSCOPICALLY DISTINGUISHABLE DI- RI02 2:03 – 2:18 ASTEREOMERS THROUGH COMPLEXATION WITH 3,3,3-TRIFLUORO-1,2-EPOXYPROPANE, Mark D. Marshall, BENZENE’S INFERNO, PART II: AUTOMATED ANALYSIS AND IDENTIFICATION, Kelvin Lee, Michael C McCarthy Helen O. Leung, Melanie Schnell, Sergio R Domingos, Anna Krin RI03 2:21 – 2:36 SiH NC NH Si RH03 2:21 – 2:36 ROTATIONAL SPECTROSCOPY OF SILICON-NITROGEN MOLECULES: 3 AND 2 , Kelvin Lee,G. THE MICROWAVE SPECTRUM AND MOLECULAR STRUCTURE OF THE CHIRAL TAGGING CANDIDATE, Stephen Kocheril, Carl A Gottlieb, Michael C McCarthy 3-FLUORO-1,2-EPOXYPROPANE (EPIFLUOROHYDRIN), AND ITS COMPLEX WITH THE ARGON ATOM, RI04 2:39 – 2:54 Mark D. Marshall, Helen O. Leung, Devon J. Stuart A HIGH SPEED FITTING PROGRAM FOR ROTATIONAL SPECTROSCOPY, Brandon Carroll, Kelvin Lee, Michael C RH04 2:39 – 2:54 McCarthy HYDROGEN BONDING IN THE MONOHYDRATES AND HOMODIMERS OF CYCLOHEXYLAMINE AND CYCLO- Intermission HEXANETHIOL, Marcos Juanes, Rizalina Tama Saragi, Alberto Lesarri, Ruth Pinacho, Jose´ Emiliano Rubio, Luca Evange- RI05 3:33 – 3:48 listi, Daniel A. Obenchain, Jens-Uwe Grabow AN EXPERIMENTALIST’S GUIDE TO ROTATIONAL CONSTANTS WITH LOW-COST THEORY, Kelvin Lee RH05 2:57 – 3:12 DISPERSION AND HYDROGEN BOND INTERACTIONS IN LARGE COMPLEXES: THE DIADAMANTHYL ETHER RI06 3:51 – 4:06 AN UPDATE ON THE THEORY OF ROTATIONAL ENERGY SURFACES, Bradley Klee CASE, Mar´ıa Mar Quesada-Moreno, Pablo Pinacho, Cristobal Perez, Marina Sekutor, Peter R. Schreiner, Melanie Schnell RI07 4:09 – 4:24 Intermission ROTATIONAL SPECTROSCOPY OF SYN AND ANTI-CLINAL PENTA-3,4-DIENENITRILE FROM 130-375 GHz, RH06 3:51 – 4:06 Vanessa L. Orr, Brian J. Esselman, Andrew N Owen, Samuel M. Kougias, R. Claude Woods, Robert J. McMahon STRUCTURES OF COMPLEXES OF CYCLOOCTANONE WITH WATER , Ecaterina Burevschi, Isabel Pena,˜ M. Eugenia RI08 4:27 – 4:42 Sanz MILLIMETER-WAVE SPECTRUM OF 2-CYANOPYRIDINE IN ITS GROUND STATE AND THE DYAD OF ITS LOW- RH07 4:09 – 4:24 EST ENERGY VIBRATIONALLY EXCITED STATES, ν30 AND ν21, P. Matisha Dorman, Brian J. Esselman, R. Claude THE COMPETITION AND COOPERATIVITY OF NON-COVALENT BONDS IN BENZOPHENONE-(H2O)1,2,3 CLUS- Woods, Robert J. McMahon TERS REVEALED BY BROADBAND MICROWAVE SPECTROSCOPY, Weixing Li, Pablo Pinacho, Mar´ıa Mar Quesada- Moreno, Melanie Schnell RI09 4:45 – 5:00 CHARACTERIZATION OF THE TRIFLUOROACETIC ANHYDRIDE MONOMER BY MICROWAVE SPEC- RH08 4:27 – 4:42 TROSCOPY, Nathan Love, CJ Smith, Anna Huff, Kenneth R. Leopold DIMERIZATION AND MICROSOLVATION OF 2- AND 3-THIOPHENEETHANOL, Marcos Juanes, Rizalina Tama Post-Deadline Abstract Saragi, Alberto Lesarri, Lourdes Enriquez, Martin Jaraiz RI10 5:03 – 5:18 PRECISION MEASUREMENT OF ULTRACOLD POLAR MOLECULES SPECTROSCOPY, Ting Gong, Zhonghao Li, Zhonghua Ji, Yanting Zhao, Yuting Liu, Liantuan Xiao, Suotang Jia 36 37 RJ. Atmospheric science RK. Mini-symposium: High-Harmonic Generation and XUV Spectroscopy Thursday, June 20, 2019 – 1:45 PM Thursday, June 20, 2019 – 1:45 PM Room: 217 Noyes Laboratory Room: B102 Chemical and Life Sciences Chair: Zachary Reed, National Institute of Standards and Technology, Gaithersburg, MD, USA Chair: Scott G Sayres, Arizona State University, Tempe, AZ, USA

RJ01 1:45 – 2:00 RK01 INVITED TALK 1:45 – 2:15 THE ATMOSPHERIC CHEMISTRY EXPERIMENT (ACE) SATELLITE: NEW PROCESSING RESULTS, TOWARD ATTO-PUMP-ATTO-PROBE SPECTROSCOPY OF ELECTRONIC DYNAMICS, Wen Li Peter F. Bernath, Chris Boone RK02 2:21 – 2:36 RJ02 2:03 – 2:18 MACROSCOPIC SIMULATION OF NEAR-THRESHOLD HIGH HARMONIC GENERATION USING MICROSCOPIC OZONE ISOTOPOLOGUE MEASUREMENTS FROM THE ATMOSPHERIC CHEMISTRY EXPERIMENT (ACE), TDSE/TDDFT CALCULATIONS, R Reiff, J Venzke, T Joyce, Andreas Becker, Agnieszka Jaron-Becker Anton Madushanka Fernando, Peter F. Bernath, Chris Boone RK03 2:39 – 2:54 RJ03 2:21 – 2:36 IDENTIFYING THE TRIPLET INTERMEDIATE STATE IN THE ULTRAFAST PHOTOINDUCED SPIN-TRANSITION INVESTIGATION OF REFERENCE SPECTROSCOPIC PARAMETERS OF WATER VAPOR IN APPLICATION TO AT- OF LOW-SPIN IRON(II) COMPOUNDS USING FEMTOSECOND M2,3-EDGE ABSORPTION SPECTROSCOPY, MOSPHERIC OBSERVATIONS IN THE 22 230 - 22 721 cm−1 REGION, Eamon K Conway, Iouli E Gordon, Kelly Chance, Kaili Zhang, Ryan T Ash, Elizabeth S Ryland, Kristopher Benke, Max A Verkamp, Ming-Fu Lin, Frank de Groot, Gregory Jonathan Tennyson S. Girolami, Josh Vura-Weis RJ04 2:39 – 2:54 RK04 2:57 – 3:12 HIGH ACCURACY LINE INTENSITIES FOR NEAR-INFRARED CARBON DIOXIDE BANDS, David A. Long, Zachary A VELOCITY MAP IMAGING ANALYSIS OF Fe(CO)5, W(CO)6 AND ELECTRON STIMULATED DESORPTION IN Reed, Adam J. Fleisher, Erin M. Adkins, Hongming Yi, Helene M Fleurbaey, Joseph Mendonca, Joseph T. Hodges Me2Au(acac), Maria Pintea, Nigel Mason, Lionel Amiaud Intermission Intermission RJ05 3:33 – 3:48 RK05 3:51 – 4:06 CRIEGEE INTERMEDIATES REACTIONS WITH FORMIC ACID PROBED BY FTMW SPECTROSCOPY, PHOTOINDUCED RING CURRENTS IN MOLECULES , Agnieszka Jaron-Becker,TJoyce Carlos Cabezas, Yasuki Endo RK06 4:09 – 4:24 RJ06 3:51 – 4:06 COINCIDENCE MEASUREMENTS OF STRONG FIELD MOLECULAR DOUBLE IONIZATION, Chuan Cheng,Patricia FTMW SPECTROSCOPY OF THE METHYL-VINYL CRIEGEE INTERMEDIATE, Yasuki Endo, Chen-An Chung, Yuan- Vindel Zandbergen, Spiridoula Matsika, Thomas Weinacht Pern Lee RK07 4:27 – 4:42 RJ07 4:09 – 4:24 PROBING THE ULTRAFAST INTERMEDIATE STATES OF A DIVALENTCO-MN COMPLEX WITH FEMTOSECOND THE REACTION OF CH2OO WITH HNO3 INVESTIGATED WITH A STEP-SCAN FTIR SPECTROMETER, M-EDGE XANES, Elizabeth S Ryland, Kaili Zhang, Clare Leahy, Josh Vura-Weis Chen-An Chung, Cho-Wei Hsu, Yuan-Pern Lee RK08 4:45 – 5:00 RJ08 4:27 – 4:42 IMAGING OF ATTOSECOND RING CURRENT DYNAMICS, J Venzke, Cory Goldsmith, Agnieszka Jaron-Becker, An- INELASTIC COLLISION DYNAMICS OF O3+Ar, Sangeeta Sur, Steve Alexandre Ndengue, Ernesto Quintas Sanchez,´ dreas Becker Richard Dawes RJ09 4:45 – 5:00 RADIATIVE CHARGE TRANSFER AND ASSOCIATION IN Ar+H+ AND Ar++H COLLISIONS, M. Bouledroua, Fatima Talhi 38 39 RL. Spectroscopy as an analytical tool FA. Astronomy Thursday, June 20, 2019 – 1:45 PM Friday, June 21, 2019 – 8:30 AM Room: 2079 Natural History Room: 116 Roger Adams Lab Chair: Neil J Reilly, University of Massachusetts Boston, Boston, MA, USA Chair: David E. Woon, University of Illinois at Urbana-Champaign, Urbana, IL, USA

RL01 1:45 – 2:00 FA01 8:30 – 8:45 STUDY OF STRENGTH VARIATIONS IN STEROIDS USING LIBS, P. K. Tiwari,A.K.Rai DETECTION OF NON-EMISSION VIBRONIC BANDS OF THIOPHENOXY RADICAL BY ABSORPTION SPEC- TROSCOPY, Haruka Sato, Mayu Negishi, Mitsunori Araki, Takahiro Oyama, Koichi Tsukiyama RL02 2:03 – 2:18 STUDY OF ELEMENTAL AND MOLECULAR EVIDENCES IN DRUGS USING LIBS, A. K. Rai,P.K.Tiwari FA02 8:48 – 9:03 + RL03 2:21 – 2:36 H3 ,THEIDEALPROBEFORIN SITU MEASUREMENT OF GALACTIC COSMIC RAYS , Takeshi Oka BASELINE-FREE MEASUREMENT OF TEMPERATURE, PRESSURE, AND CONCENTRATION FROM MOLECU- FA03 9:06 – 9:21 LAR FREE INDUCTION DECAY, Ryan K. Cole, Amanda S. Makowiecki, Nazanin Hoghooghi, Gregory B Rieker + H3 IN THE EARLY UNIVERSE, Yu-Shan M. Chen, Takeshi Oka RL04 2:39 – 2:54 FA04 9:24 – 9:39 HIGH RESOLUTION COHERENT 2D AND 3D SPECTROSCOPY , Peter Chen, Thresa Wells ROVIBRATIONAL STUDY OF HNCS PRODUCED VIA ELECTRIC DISCHARGE IN A NEWLY CONSTRUCTED RL05 2:57 – 3:12 MULTIPASS IR CELL AT THE CANADIAN LIGHT SOURCE SYNCHROTRON, Jennifer van Wijngaarden, Aimee Bell, IMPLICATIONS OF SELF-PHASE MODULATION (SPM) FOR N2 FEMTOSECOND COHERENT ANTI-STOKES RA- Wenhao Sun, Brant E. Billinghurst MAN SCATTERING (FS CARS) SPECTROSCOPY AT ELEVATED PRESSURE, Mingming Gu,AmanSatija,RobertP. Intermission Lucht FA05 10:18 – 10:33 RL06 3:15 – 3:30 LINE POSITIONS FOR THE ν2 AND ν4 BANDS OF THE 5 ISOTOPOLOGUES OF GERMANE, Cyril Richard,F.Kwabia NEAR-INFRARED MOLECULAR SPECTROSCOPY USING NICE-OHMS WITH HIGH FINESSE CAVITY, Tchana, Jean Vander Auwera, Athena Rizopoulos, Vincent Boudon TzuLing Chen,YiWeiLiu FA06 10:36 – 10:51 Intermission H2O ATOMIZATION ENERGY WITH AN aug-cc-pV10Z BASIS SET, Nikesh S. Dattani RL07 4:09 – 4:24 FA07 10:54 – 11:09 MOLECULAR COMPOSITION OF GALLBLADDER STONE USING PHOTOACOUSTIC SPECTROSCOPY, A. K. Rai, A VARIATIONALLY COMPUTED T =300 K LINE LIST FOR THE METHYL RADICAL CH3, Ahmad Y. Adam, Andrey Zainab Gazali, P. K. Tiwari, Surya Narayan Thakur Yachmenev, Sergei N. Yurchenko, Per Jensen RL08 Post-Deadline Abstract 4:27 – 4:42 FA08 11:12 – 11:27 OBSERVATION OF SOME Ω=1/2 ELECTRONIC STATES OF NICKEL DEUTERIDE, NiD, WITH LASER-INDUCED THE 135 – 375 GHZ ROTATIONAL SPECTRUM OF BENZOISONITRILE, AN ISOMER OF THE FIRST INTERSTEL- FLUORESCENCE, Amanda J. Ross, Patrick Crozet, Allan G. Adam, Dennis W. Tokaryk LAR BENZENE DERIVATIVE DETECTED BY RADIOASTRONOMY, Maria Zdanovskaia, Brian J. Esselman, R. Claude Woods, Robert J. McMahon RL09 4:45 – 5:00 3D MOMENTUM IMAGING OF LASER DESORPTION IONIZATION OF 2,5-DIHYDROXYBENZOIC ACID (DHB), Gabriel A. Stewart, Duke A. Debrah, Gihan Basnayake, Wen Li RL10 5:03 – 5:18 ELECTROCHEMICAL SURFACE-ENHANCED RAMAN SPECTRA AND PLASMON-DRIVEN PHOTOELECTRO- CHEMICAL REACTION OF P-AMINOTHIOPHENOL ON SILVER ELECTRODE OF NANOSTRUCTURES, Meng Zhang, De-Yin Wu, Zhong-Qun Tian 40 41 FB. Atmospheric science FC. Clusters/Complexes Friday, June 21, 2019 – 8:30 AM Friday, June 21, 2019 – 8:30 AM Room: 100 Noyes Laboratory Room: 1024 Chemistry Annex Chair: Jacob Stewart, Connecticut College, New London, CT, USA Chair: Christopher J. Johnson, Stony Brook University, Stony Brook, NY, USA

FB01 Post-Deadline Abstract 8:30 – 8:45 FC01 8:30 – 8:45 CHARACTERIZATION OF HYDROPEROXYMETHYL FORMATE BY MICROWAVE SPECTROSCOPY: MOLECU- HYDROGEN BOND NETWORKS IN THE SOLVATION OF THE SIMPLEST SUGAR, Cristobal Perez, Amanda Steber, LAR INSIGHT INTO AEROSOL FORMATION, Jessie P Porterfield, Kelvin Lee, Valentina Dell’Isola, Brandon Carroll, Melanie Schnell Michael C McCarthy FC02 8:48 – 9:03 FB02 8:48 – 9:03 IR SPECTROSCOPY OF GLYCINE-WATER CLUSTERS IN HELIUM NANODROPLETS, Nitish Pal, Devendra Mani, MEASUREMENT OF VOCs USING OPEN-PATH MID-INFRARED DUAL-COMB SPECTROSCOPY, Kevin C Cossel, Raffael Schwan, Tarun Kumar Roy, Gerhard Schwaab, Britta Redlich, Lex van der Meer, Martina Havenith Gabriel Ycas, Fabrizio Giorgetta, Esther Baumann, Jacob T Friedlein, Daniel I. Herman, Eleanor Waxman, Ian Coddington, FC03 9:06 – 9:21 Nathan R. Newbury IR-INDUCED CHANGE IN THE MICROSCOPIC HYDRATION STRUCTURES OF PHENOL CATIONS TRAPPED IN FB03 9:06 – 9:21 THE COLD ION TRAP, Hikaru Sato, Yasutoshi Kasahara, Haruki Ishikawa A K-BAND MICROWAVE SPECTROMETER FOR STUDYING ATMOSPHERIC REACTIONS, Chris Medcraft FC04 9:24 – 9:39 FB04 9:24 – 9:39 FRANCK-CONDON-LIKE PATTERNS OBSERVED IN THE INFRARED SPECTRA OF PHENOL-ALKYLSILANE DEVELOPMENT AND PERFORMANCE OF LILLE’S FOURIER TRANSFORM MILLIMETER-WAVE SPECTROME- DIHYDROGEN-BONDED CLUSTERS IN THE EXCITED STATES, Masaaki Uchida, Takutoshi Shimizu, Yasutoshi Kasa- TER , Luyao Zou, R. A. Motiyenko, L. Margules,` E. A. Alekseev hara, Yoshiteru Matsumoto, Haruki Ishikawa Intermission FB05 9:42 – 9:57 CONFORMATIONAL LANDSCAPE OF 3-METHOXYPHENOL INVESTIGATED BY JET-COOLED HIGH RESOLU- FC05 10:18 – 10:33 TION INFRARED SPECTROSCOPY , Pierre Asselin, Yacine Belkhodja, Yann Berger, Jonas Bruckhuisen, Arnaud Cuisset PLANAR ION FUNNEL FOR IMPROVED CONTROL OF ION TRANSMISSION AND TEMPERATURE IN CLUSTER Intermission STUDIES, Carley N Folluo, Abbey McMahon, Jarrett Mason, Caroline Chick Jarrold FB06 10:36 – 10:51 FC06 10:36 – 10:51 DEMONSTRATION OF A 180 GHZ FULL CMOS SPECTRALLY DISPERSED HETERODYNE RADIOMETER WITH DIMERIZATION EFFECT ON HF ELIMINATION FROM THE PHOTOIONIZED FLUOROPHENOLS, Piyali Chatterjee, InP LNA FOR REMOTE SENSING, Deacon J Nemchick, Brian Drouin, Adrian Tang, Yanghyo Kim, Theodore J Reck, Souvick Biswas, Tapas Chakraborty Maria Alonso, Goutam Chattopadhyay, Yan Zhang, M.-C. Frank Chang FC07 10:54 – 11:09 + FB07 10:54 – 11:09 INFRARED SPECTROSCOPY OF [(H2S)2(X)1] (X = WATER, METHANOL, AND ETHANOL): INFLUENCE OF THE SUB-DOPPLER INFRARED SPECTROSCOPY OF JET COOLED CH2Br RADICAL: CH2 STRETCH VIBRATIONS, MICROSOLVATION ON THE HEMIBOND, Keigo Hattori, Dandan Wang, Asuka Fujii Andrew Kortyna, Kirstin D Doney, Preston G. Scrape, David Nesbitt FC08 11:12 – 11:27 FB08 11:12 – 11:27 MEASURING THE ELECTRONIC ABSORPTION SPECTRA OF GOLD NANOCLUSTERS VIA MASS SELECTIVE HIGH-RESOLUTION INFRARED SPECTRA AND ANALYSES OF SiF4, Vincent Boudon, Laurent Manceron UV-VIS SPECTROSCOPY, Hanna Morales Hernandez, Anthony Cirri, Christina Kmiotek, Christopher J. Johnson FB09 11:30 – 11:45 ULTRAVIOLET PHOTOABSORPTION OF SO ISOTOPOLOGUES AND THE B 3Σ− AND C 3Π STATES, Alan Heays, Glenn Stark, James R Lyons, Nelson de Oliveira, Brenton R Lewis, Stephen T Gibson 42 43 FD. Radicals FE. Lineshapes, collisional effects Friday, June 21, 2019 – 8:30 AM Friday, June 21, 2019 – 8:30 AM Room: 217 Noyes Laboratory Room: B102 Chemical and Life Sciences Chair: Laura R. McCunn, Marshall University, Huntington, WV, USA Chair: Shanshan Yu, California Institute of Technology, Pasadena, CA, USA

FD01 8:30 – 8:45 FE01 8:30 – 8:45 INFRARED SPECTRA OF THE 2,3-DIHYDROPYRROL-2-YL AND 2,3-DIHYDROPYRROL-3-YL RADICALS ISO- ORIENTATIONAL ANISOTROPY INDUCED INHOMOGENEOUS LINE BROADENING IN THE ROVIBRATIONAL LATED IN SOLID PARA-HYDROGEN, Jay C. Amicangelo, Yuan-Pern Lee SPECTRA OF CYANOACETYLENE SOLVATED IN HELIUM DROPLETS, OR: HOW I LEARNED TO STOP WORRY- ING AND LOVE THE PROVERBIAL DROPLET EFFECTS, Peter R. Franke, Gary E. Douberly FD02 8:48 – 9:03 MATRIX-ISOLATION FTIR SPECTROSCOPY OF THE DEHYDRO-PYRAZINE RADICAL, Mayank Saraswat, Sugumar FE02 8:48 – 9:03 Venkataramani ULTRAVIOLET SPECTROSCOPY OF SUPERCRITICAL CARBON DIOXIDE, Timothy W Marin, Ireneusz Janik FD03 9:06 – 9:21 FE03 9:06 – 9:21 LASER-INDUCED FLUORESCENCE STUDY OF JET-COOLED TUNGSTEN MONOXIDE (WO) IN GAS PHASE, PHOTOACOUSTIC SPECTROSCOPY OF THE O2 A-BAND IN SUPPORT OF REMOTE SENSING, Elizabeth M Lunny, Jie Yang, Jicai Zhang, Xinwen Ma Matthew J. Cich, Thinh Quoc Bui, David A. Long, Joseph T. Hodges, Brian Drouin, Mitchio Okumura FD04 9:24 – 9:39 FE04 9:24 – 9:39 VISIBLE VIBRONIC EMISSION SPECTROSCOPY OF JET-COOLED BENZYL-TYPE RADICALS GENERATED FT-IR MEASUREMENTS OF O2 COLLISION-INDUCED ABSORPTION IN THE 565 – 700 NM REGION USING A FROM 4-CHLORO-M-XYLENE, Sang Lee HIGH PRESSURE GAS ABSORPTION CELL, Keeyoon Sung, Edward H Wishnow, Timothy J. Crawford, Deacon J Nem- Intermission chick, Brian Drouin, Shanshan Yu, Vivienne H Payne, Jonathan H Jiang FE05 9:42 – 9:57 FD05 10:18 – 10:33 NUMERICAL EVALUATION OF HARTMANN-TRAN LINE PROFILE USE IN SYNTHETIC, NOISY SPECTRA, IONIZATION ENERGIES AND SINGLE VIBRONIC LEVEL EMISSION (SVLE) SPECTROSCOPY OF CIS- AND Erin M. Adkins, Joseph T. Hodges TRANS-1-VINYLPROPARGYL RADICALS, Jonathan Flores, Meredith Ward, Sederra D. Ross, Neil J Reilly Intermission FD06 10:36 – 10:51 IDENTIFYING AN UNKNOWN ISOMER OF C7H7 OBSERVED IN JET-COOLED HYDROCARBON DISCHARGES, FE06 10:36 – 10:51 Meredith Ward, Jonathan Flores, Sederra D. Ross, Laura M McCaslin, John F. Stanton, Neil J Reilly HIGH TEMPERATURE METHANE LINE BROADENING BY H2, Mahdi Yousefi, Peter F. Bernath, Michael Dulick FE07 10:54 – 11:09 FD07 10:54 – 11:09 HIGH-ACCURACY HIGH-TEMPERATURE PRESSURE BROADENING AND LINE POSITIONS FOR MODELING ELECTRONIC STRUCTURE OF OH·ISOPRENE ADDUCTS FROM ANION PHOTOELECTRON IMAGING SPEC- H2O AND CH IN EXOPLANET ATMOSPHERES, Ehsan Gharib-Nezhad, Alan Heays, James R Lyons, Michael R Line, TROSCOPY, Marissa A. Dobulis, Michael C Thompson, Kellyn M. Patros, Caroline Chick Jarrold 4 Hans A Bechtel FD08 11:12 – 11:27 FE08 11:12 – 11:27 ANION PHOTOELECTRON IMAGING SPECTROSCOPY OF REACTION INTERMEDIATES IN THE OZONOLYSIS TEMPERATURE-DEPENDENCE OF SELF- AND AIR-BROADENED CO LINE SHAPES IN THE FUNDAMENTAL OF ISOPRENE, Marissa A. Dobulis, Michael C Thompson, Caroline Chick Jarrold BAND, Adriana Predoi-Cross, Nazrul Islam, Mary Ann H. Smith, V. Malathy Devi, Sergei V Ivanov, Franck Thibault FE09 11:30 – 11:45 INVESTIGATION OF ORTHO-PARA-DEPENDENT PRESSURE BROADENING IN THE ν1 + ν3 BAND OF ACETY- LENE, Eisen C. Gross, Trevor Sears 44 45 FF. Comparing theory and experiment MA. Plenary Friday, June 21, 2019 – 8:30 AM Monday, June 17, 2019 – 8:30 AM Room: 2079 Natural History Room: Foellinger Auditorium Chair: Jinjun Liu, University of Louisville, Louisville, KY, USA Chair: Martin Gruebele, University of Illinois at Urbana-Champaign, Urbana, IL, USA

FF01 8:30 – 8:45 STRETCHING OUR KNOWLEDGE OF THE ELECTRONIC GROUND STATE OF C3: THE SPECTROSCOPY OF STRETCHING MODES OF C3, Kirstin D Doney, Benjamin Schroder,¨ Dongfeng Zhao, Peter Sebald, Harold Linnartz FF02 8:48 – 9:03 Welcome 8:30 MOMENTUM DICTATES INTENSITY: UNUSUAL OBSERVATIONS IN PHOTOELECTRON SPECTROSCOPY, Feng Sheng Hu, Dean of the College of Liberal Arts & Sciences Jarrett Mason, Josey E Topolski, Joshua C Ewigleben, Srinivasan S. Iyengar, Caroline Chick Jarrold University of Illinois at Urbana-Champaign FF03 9:06 – 9:21 MODELING ELECTRON DETACHMENT FROM METAL OXIDE CLUSTERS WITH EFFICIENT ELECTRONIC MA01 8:40 – 9:20 STRUCTURE METHODS, Hrant P Hratchian LASER COOLING OF MOLECULES: TOWARDS ULTRACOLD SYMMETRIC AND CHIRAL SPECIES FF04 9:24 – 9:39 12 NON-RESONANT RAMAN SPECTRA OF THE METHYL RADICAL CH3 SIMULATED IN VARIATIONAL CALCU- JOHN M. DOYLE, Department of Physics, Harvard University, Cambridge, MA, USA. LATIONS, Ahmad Y. Adam, Andrey Yachmenev, Sergei N. Yurchenko, Per Jensen FF05 9:42 – 9:57 Ultracold molecules are a promising platform for diverse scientific goals, ranging from quantum information and simu- ANALYZING THE ROTATIONAL AND SPIN STRUCTURE OF THE TWO LOWEST ELECTRONIC STATES OF lation to controlled chemistry and precision measurements of fundamental physics. The rich internal structure of molecules, ASYMMETRICALLY SUBSTITUTED ALKOXY RADICALS, Yi Yan, Terry A. Miller, Jinjun Liu including vibrations, rotations, and hyperfine interactions, provides many handles for exquisite control. However, the very Intermission same structural features that make molecules so desirable to study also complicate the task of controlling a molecular species. Recently, laser cooling and magneto-optical trapping of diatomic molecules has been realized by several groups around the FF06 10:36 – 10:51 world, leading to temperatures as low as a few μK in long-lived, trapped samples of CaF. The ability to laser cool also allows ANALYSIS OF PSEUDO-JAHN-TELLER EFFECT IN METAL ALKOXIDES, Ketan Sharma, Terry A. Miller, Anam C. for high fidelity detection of ultracold molecules and increases in phase space density allowing, e.g., the study of ultracold Paul, Jinjun Liu molecular collisions. As our group has shown with SrOH, these cooling methods apply to a broad and generic class of FF07 10:54 – 11:09 molecules, including polyatomic species which offer significant and qualitatively new advantages over any diatomic species. CALCULATING ROTATIONAL SIGNATURES FOR JAHN-TELLER DISTORTED MOLECULES, Ketan Sharma,Scott For example, polyatomic molecules may be fully polarized at extremely low electric fields and provide longer coherence M. Garner, Terry A. Miller, John F. Stanton times, allowing one to probe physics Beyond the Standard Model at the PeV scale. Importantly, the presence of these addi- FF08 11:12 – 11:27 tional states in polyatomics does not interfere with the laser cooling process already observed in simpler species. In this talk, TUNNELING REACTIONS OF HYDROGEN ADDITION TO PROPENE IN A SOLID PARA-HYDROGEN MATRIX, I will outline the experimental goal of creating ultracold gases of polyatomic molecules using illustrative examples from our Gregory T. Pullen, Peter R. Franke, Gary E. Douberly, Karolina Anna Haupa, Yuan-Pern Lee laser cooling of CaF and SrOH molecules. I will also present how we will extend the techniques already demonstrated to chiral molecules, whose asymmetry presents novel challenges but also exciting new possibilities.

MA02 9:25 – 10:05 PROTEIN CHARACTERIZATIONS BY CHIRAL VIBRATIONAL SUM FREQUENCY GENERATION SPEC- TROSCOPY

ELSA YAN, Chemistry, Yale University, New Haven, CT, USA.

Characterization of protein structures at interfaces in situ and in real time is important to solve fundamental and engi- neering problems. Nonetheless, such characterization remains challenging because it requires methods to be both selective to interfaces and protein structures. We show that chiral vibrational sum frequency generation spectroscopy (SFG) can provide peptide amide I and N-H stretching vibrational signals that are free of water background and characteristic to parallel beta- sheet, anti-parallel beta-sheet, alpha-helix, 3-10 helix, and disordered structures, thus enabling characterization of protein secondary structures at interfaces, similar to circular dichroism for characterizing protein structures in solution. Using chiral SFG, we monitor misfolding of an amyloid protein, measure interfacial protein orientation, derive new methods for prob- ing backbone proton exchange, and examine two-dimensional crowding effects on protein folding. Moreover, we observe chiral SFG stretching modes of water molecules associated with a beta-sheet protein. This result reveals that achiral water molecules can be organized by the protein into chiral supermolecular structures. The result also implies that chiral SFG can be a promising vibrational probe for water structures in protein hydration. These recent developments demonstrate that chiral SFG can provide an array of new tools for addressing biological and biomedical problems related to protein structures.

Intermission 46 47

MA03 10:40 – 11:20 MA05 11:50 – 12:05 THE RENAISSANCE OF ROTATIONAL SPECTROSCOPY: THEORY MEETS EXPERIMENT FOR NEW CHAL- ELECTRONIC SPECTROSCOPY OF MASS-SELECTED LIGAND-PROTECTED METAL NANOCLUSTERS LENGES CHRISTOPHER J. JOHNSON, Chemistry, Stony Brook University, Stony Brook, NY, USA. CRISTINA PUZZARINI, Dep. Chemistry ’Giacomo Ciamician’, University of Bologna, Bologna, Italy. Nanostructured particles hold much promise as “designer materials,” but full realization of this promise requires a detailed Among different spectroscopic techniques, rotational spectroscopy, given its intrinsic high resolution and high sensitivity, understanding of the geometric and electronic effects driving their behavior. While some smaller particles, often called is one of the most powerful tools for investigating the structure and dynamics of molecules and supramolecular systems in the nanoclusters, can be synthesized monodispersely and crystallized to determine their geometric structures, this is not generally gas phase. Rotational spectra contain a wealth of accurate information on structural, molecular, and spectroscopic parameters true and no similarly powerful technique exists for the determination of their electronic structures. We have extended mass- that are difficult or impossible to obtain by other experimental techniques. However, the task of extracting information selective action spectroscopy techniques to small ligand-protected metal nanoclusters synthesized using standard solution- from the analysis of the spectral features is challenging, time-consuming, and prone to errors. In the last decade, rotational phase protocols. These clusters are mass-selected from a mixture and stored in a variable-temperature ion trap where they spectroscopy has experienced huge technological improvements that have led to a revitalization of the field, also due to adsorb weakly-bound “tag” molecules that act both as action spectroscopy messengers and a mildly perturbative environment. parallel advancements in theoretical methods and computational resources. These experiments reveal dramatically more information than do typical UV/Vis spectra in solution, likely at the limit of Given these advances, the interplay of theory and experiment in rotational spectroscopy is discussed by means of repre- resolution considering lifetime effects and the high density of states of the clusters. We find that minor functionalization of sentative examples that vividly illustrate what can be accomplished with theory and experiment brought together in this field. the protecting ligands has a drastic impact on the cluster electronic structure, even for transitions between two nominally In particular, it will be shown how such an interplay can be exploited to address new challenges, exemplified by studying the metal-based states. Even more surprisingly, very subtle environmental effects, such as solvation by He or N2, yield notable nature of weak interactions in molecular adducts where the bonding pairs are made up of non-hydrogen atoms. Another fasci- shifts to the spectra, suggesting that even weakly interacting ligands and solvents can have major effects. Taken together, nating challenge is offered by the open issues posed by astrochemistry. Astronomical observations of rotational spectroscopy these spectra provide the first experimental windows into using subtle chemical effects to tune the properties of these clusters signatures provide the unequivocal proof of the presence of chemical species in the astronomical source under consideration, for chemical and technological applications. and the talk will also explore the degree to which rotational spectroscopy can assist in going beyond the “simple” identification of interstellar species.

FLYGARE AWARDS 11:25 Introduction by Yunjie Xu, University of Alberta

MA04 11:30 – 11:45 MICROWAVE SPECTROSCOPY AT MISSOURI S&T

G. S. GRUBBS II, Department of Chemistry, Missouri University of Science and Technology, Rolla, MO, USA.

At the Missouri University of Science and Technology we are interested in developing tools and techniques to obtain new understanding and disseminate knowledge about molecular rotational spectra. We accomplish these ends by researching new ways to attack microwave spectroscopic problems both in the research and teaching laboratories. Some of the problems we are interested in involve providing research-grade microwave teaching tools to students with limited financial resources, O2 van der Waals complexes and the complexities of spin coupling, and trying to identify new approaches for chiral molecule analysis using the microwave technique. Because many of our spectroscopic studies employ the CP-FTMW technique, we are also developing methodologies to improve the sensitivity of this instrument through instrumental design. This talk will provide a brief overview of each of these topics and some of the progress we have made. 48 49 MG. Mini-symposium: Astrochemistry and Astrobiology in the age of ALMA Monday, June 17, 2019 – 1:45 PM MG03 2:39 – 2:54 DETECTION OF CH3CN IN THE ENVELOPE AROUND SAGITTARIUS B2(N) Room: 116 Roger Adams Lab MITSUNORI ARAKI, Research Institute for Science and Technology, Tokyo University of Science, Noda, Japan; Chair: Brett A. McGuire, National Radio Astronomy Observatory, Charlottesville, VA, USA SHURO TAKANO, College of Engineering, Nihon University, Fukushima, Japan; TAKAHIRO OYAMA, Fac- ulty of Science Division I, Tokyo University of Science, Shinjuku-ku, Tokyo, Japan; NOBUHIKO KUZE, Faculty of Science and Technology, Sophia University, Tokyo, Japan; KAZUHISA KAMEGAI, , National Astronomical Observatory of Japan, Tokyo, Japan; KOICHI TSUKIYAMA, Faculty of Science Division I, Tokyo University of Science, Shinjuku-ku, Tokyo, Japan.

Traditionally used model of evolution of molecular clouds in interstellar space is described as increasing of cloud gas MG01 1:45 – 2:00 density from diffuse to dense conditions, i.e., from an atomic-gas cloud to a star-forming region via a diffuse cloud and a THE ATACAMA LARGE MILLIMETER/SUBMILLIMETER ARRAY - FROM EARLY SCIENCE TO FULL OPERA- dense cloud. However, reverse evolution of molecular clouds is suggested by Price et al. [1]. For example, outflow from TIONS. a star-forming region makes a relatively-low-density cloud. To find a clue of reverse evolution, investigation of chemical composition of relatively-low-density clouds is necessary. Rotational transitions of CH3CN can be observed by absorption, ANTHONY REMIJAN, NAASC, National Radio Astronomy Observatory, Charlottesville, VA, USA. and they can be analyzed by using a model of the hot axis effect, which shows special rotational distributions of CH3CN in a relatively-low-density cloud [2]. In our previous work, CH3CN was detected via absorption lines of the J = 4–3 rotational The Atacama Large Millimeter/Submillimeter Array (ALMA) is now entering its 8th cycle of scientific observations - transition in the envelope of Sagittarius B2(M) core in the Galactic Center region by using Nobeyama 45-m telescope [3]. starting with Cycle 0 in 2011. Cycle 7 should be one the last cycles that is considered ”Steady State” Operations. With the In this work, using ALMA data archive [4], we investigated absorption lines of the J = 5–4 and 6–5 rotational transitions of commissioning of new capabilities over the next several years including wide field polarization, continuum single dish, new CH3CN in the envelope of Sagittarius B2(N) core, which is an adjacent core of the (M) core. The column density of CH3CN receiver bands and high frequency observations at long baselines, ALMA will begin ”Full Science” operations. In addition, in the envelope of the (N) core is derived to be (1.0 ± 0.2) × 1015 cm−2, which is 7 times larger than that in the envelope of ALMA is approaching completion of its initially envisaged capabilities and, within the first five years of operations, the orig- the (M) core, while the (N) core has an 11-times larger column density than the (M) core [5]. Similar abundance relation was inal fundamental science goals of ALMA have been essentially achieved. As such, a new ALMA Development Roadmap has found in the case of HC3N. Thus, as chemical compositions of relatively-low-density clouds, it was found that an abundant been published that highlights the new fundamental science drivers for ALMA as we start the second decade of ALMA op- core has an abundant envelope and vice versa in the Sagittarius B2 region. To investigate reverse evolution, we will analyze erations (https://www.almaobservatory.org/wp-content/uploads/2018/07/20180712-alma-development-roadmap.pdf). In this additional molecules from now on. talk, I will detail the upcoming ALMA Cycle 7 observing capabilities, describe the process of selecting new observing modes [1] Price et al., 2003, MNRAS, 343, 1257. [2] Araki et al., Astronomical Journal, 148, 87 (2014). [3] Araki et al., JpGU for upcoming cycles and provide an update on the status of the ALMA Full Science capabilities including a brief description 2018, PPS09-01. [4] Project Code: 2016.1.00074.S. [5] Belloche et al., 2013, A&A, 559, 47 of the new fundamental science drivers for ALMA.

MG04 2:57 – 3:12 EXPLORING MOLECULAR COMPLEXITY WITH ALMA (EMOCA): COMPLEX ISOCYANIDES IN SGR B2(N) INVITED TALK MG02 2:03 – 2:33 ERIC R. WILLIS, Department of Chemistry, The University of Virginia, Charlottesville, VA, USA;ROBINT. EXPLORING THE COMPLEX CHEMISTRY OF EMBEDDED PROTOSTARS GARROD, Departments of Chemistry and Astronomy, The University of Virginia, Charlottesville, VA, USA; ARNAUD BELLOCHE, Millimeter- und Submillimeter-Astronomie, Max-Planck-Institut fur¨ Radioastronomie, JES JORGENSEN, Centre for Star and Planet Formation, Niels Bohr Institute and Natural History Museum of Bonn, NRW, Germany; HOLGER S. P. MULLER,¨ I. Physikalisches Institut, Universitat¨ zu Koln,¨ Koln,¨ Germany; Denmark, University of Copenhagen, Copenhagen, Denmark. KARL M. MENTEN, Millimeter- und Submillimeter-Astronomie, Max-Planck-Institut fur¨ Radioastronomie, Bonn, NRW, Germany. One of the most important problems of astrochemistry is to understand how, when and where complex organic and potentially prebiotic molecules are formed - and what is the link between the rich chemistry observed toward some star- The EMoCA survey is a spectral line survey using the Atacama Large Millimeter/submillimeter Array (ALMA) to study forming regions and the emerging Solar System. From an observational point of view, ALMA is revolutionizing the field the hot-core complex Sagittarius B2(N). Recently, EMoCA revealed the presence of 5 hot cores in this complex, including with its high sensitivity for faint lines, high spectral resolution limiting line confusion, and high angular resolution making it N2, which is a rich source for the study of complex molecules due to its narrow linewidths. We seek to analyze data from possible to study the structure of young protostars down to scales of their emerging protoplanetary disks. the EMoCA survey to investigate the column densities and excitation temperatures of nitrile and isonitrile (i.e., cyanide and In this talk, I will discuss recent results on the chemistry of young solar-type protostars with ALMA. I will focus on a isocyanide) species. We report the first detection of CH3NC and HCCNC in Sgr B2(N2). In addition, we calculate new + large ALMA survey of the low-mass protostellar binary and astrochemical template source, IRAS 16293-2422. The program, upper limits for C2H5NC, C2H3NC, HNC3 and HC3NH . We then use the coupled three-phase chemical kinetics code ”Protostellar Interferometric Line Survey (PILS)”, is more than an order of magnitude more sensitive than previous surveys MAGICKAL to simulate their chemistry. Several new species, and over 100 new reactions have been added to the network. In of chemical complexity and provide images of the inner 25 AU of the gas around each of the young stars. The high sensitivity addition, a new single-stage collapse/warm-up model has been implemented, thus eliminating the need for the previous two- and spectral resolution of ALMA have led to the detection of a wealth of species for the first time toward solar-type protostars stage models. A variable, visual extinction-dependent ζ is also incorporated into the model. Our updated chemical models as well as the ISM in general - for example, molecules of importance for prebiotic chemistry such as peptide-bond containing do a reasonable job of reproducing the abundance ratios of the various isocyanide/cyanide pairs, with the best-fit model species and simple sugars. Also, the data show the presence of numerous rare isotopologues of complex organic molecules having an enhanced cosmic-ray ionization rate. Radiative transfer models are run on the best-fit chemical model. Column and other species: the exact measurements of the abundances of these isotopologues shed new light onto the formation of such densities produced by the radiative transfer models are lower than those determined observationally. Excitation temperatures complex species and provide a chemical link between the embedded protostellar stages and our own Solar System including are reproduced for some molecules, but not others, indicating there is still work to be done on the model. The new single-stage the composition of comets. Finally, I will discuss some of the issues encountered dealing with these complex datasets with chemical model should be a useful tool in analyzing other hot-core sources in the future. spectra reaching the confusion limit and providing new challenges for laboratory spectroscopy.

Intermission 50 51

MG05 3:51 – 4:06 MG08 4:45 – 5:00 THE INTERACTION OF COSMIC RAYS WITH GALACTIC CENTER MOLECULAR CLOUDS INTERSTELLAR FORMALDEHYDE - A RETROSPECTIVE

FARHAD YUSEF-ZADEH, Physics and Astronomy, Northwestern University, Evanston, IL, USA. ANTHONY REMIJAN, NAASC, National Radio Astronomy Observatory, Charlottesville, VA, USA; LEWIS E. SNYDER, Department of Astronomy, University of Illinois at Urbana-Champaign, Urbana, IL, USA;PHILIP Recent observations indicate that the cosmic rate ionization rate in the Galactic center is higher than elsewhere in the JEWELL, ALMA, National Radio Astronomy Observatory, Charlottesville, VA, USA;FRANKJLOVAS,Sensor Galaxy by one to two orders of magnitudes. These measurements are based on infrared H3+ molecular spectroscopy studies. Science Division, National Institute of Standards and Technology, Gaithersburg, MD, USA. This interaction explains the ubiquitous warm molecular gas observed throughout the Galactic center as well as the unusual chemistry of molecular gas, as indicated by the high abundance of methanol, SiO and HCO+/HCN intensity ratios. I will On 31 March 1969, the era of modern radio astrochemistry started with the detection of interstellar formaldehyde present preliminary results of two molecular line surveys of the Galactic center that we have carried out using the CSO (H2CO). It was the first detection at radio wavelengths of a molecule with more than one heavy atom (previous detections and ALMA. In particular, we discuss the intensity ratios of several molecular lines in the context of cosmic ray driven gas up until this discovery were limited to hydrogen atoms attached to a single heavy atom, e.g. CH, OH or NH3) and, with chemistry. the improvements in radio frequency receivers and new astronomical facilities coming online, heralded an era of discovery that has lasted for now more than 50 years. During this time, the number of new molecule detections has remained nearly constant at 3.7 molecules/year with a vast majority of these discoveries taking place in the radio regime (McGuire, B. 2018, APJS, 239, 17). This presentation will take us back to the time of this first detection, a quick synopsis of how observations of formaldehyde has led to a better understanding of the physical and chemical environments of astronomical sources and finally MG06 4:09 – 4:24 a look to the future with recent Green Bank Telescope (GBT) and Karl G. Jansky Very Large Array (VLA) observations of AN ALMA SEARCH FOR CHIRAL MOLECULES TOWARD SGRB2(N) the 4830 MHz transition and high frequency searches with the Atacama Large Millimeter/submillimeter Array (ALMA). BRANDON CARROLL, Atomic and Molecular Physics, Harvard-Smithsonian Center for Astrophysics, Cam- bridge, MA, USA; BRETT A. McGUIRE, NAASC, National Radio Astronomy Observatory, Charlottesville, VA, USA; GEOFFREY BLAKE, Division of Chemistry and Chemical Engineering, California Institute of Technol- ogy, Pasadena, CA, USA.

We have recently reported the first detection of a chiral molecule in the interstellar medium, toward Sgr B2(N) (McGuire & Carroll et al. 2016). Chiral molecules represent a critical class of organic species that drive biology. The cosmic origin of these species is proposed to have its origins in cometary and asteroidal material. The initial detection of propylene oxide was in the cold outer envelope of Sgr B2, however it is not clear how representative this population is of the more evolved hot core chemistry, which seeds planetesimal inventories, and the detection lacks any information on spatial distribution. Thus, propylene oxide, as well as several isotopically chiral species such as CH3CHDCN and CH3CHDOH, may persist through the hot core phase of star formation. In order to determine under what conditions chiral species might be incorporated into icy material in pre-solar environ- ments, it is necessary to map the distribution of these species.To this end, we have conducted ALMA Band 7 observations of Sgr B2(N).We will present results of our observations, and discuss the abundance and excitation conditions of propylene oxide and other isotopically chiral species.

MG07 4:27 – 4:42 + EXTENDING THE MILLIMETER/SUB-MILLIMETER SPECTRUM OF PROTONATED FORMALDEHYDE (H2COH ) FOR COMPARISON TO ASTRONOMICAL DATA

CONNOR J. WRIGHT, KEVIN ROENITZ, JAY A KROLL, SUSANNA L. WIDICUS WEAVER, Department of Chemistry, Emory University, Atlanta, GA, USA.

Molecular ions have long been known to drive rich, complex chemistry in the interstellar medium (ISM). Of partic- + ular interest is the protonated formaldehyde ion (H2COH ) as it is the main reactant in the formation and destruction of + formaldehyde (H2CO) and a precursor to protonated methanol (H3COH2 ) as well as the simplest amino acid, glycine (NH2CH2COOH). Using a pulsed supersonic expansion discharge source to produce the ion, the expansion was probed with millimeter/sub-millimeter light. The known 30,3 ← 20,2 transition at 190079.131 MHz has been previously detected in our lab utilizing a multipass optical set-up and the fast-sweep technique. However, in an effort to increase the signal-to-noise ratio of the transition with fewer averages, the experimental set up was changed and the signal has not been recovered. Here we will present the status of the experiment and the results obtained thus far in the context of the experimental design and possible future improvements. Once this transition is detected again, the spectrum will be extended past 385 GHz up to 1 THz and compared to astronomical observations in order to more confidently determine its presence in the ISM and to provide a spectral catalog that can guide future high frequency observations. 52 53 MH. Mini-symposium: Non-covalent Interactions Monday, June 17, 2019 – 1:45 PM MH04 2:39 – 2:54 Room: 100 Noyes Laboratory SYNTHESIS, MICROWAVE SPECTRA, X-RAY STRUCTURE AND HIGH-LEVEL CALCULATIONS FOR FORMAMI- DINIUM FORMATE Chair: Mark D. Marshall, Amherst College, Amherst, MA, USA ZUNWU ZHOU, STEPHEN G. KUKOLICH, Department of Chemistry and Biochemistry, University of Ari- zona, Tucson, AZ, USA; R. ALAN AITKEN, EaStCHEM School of Chemistry, University of St.Andrews, St. Andrews, United Kingdom; MICHAEL H. PALMER, School of Chemistry, University of Edinburgh, Edinburgh, MH01 1:45 – 2:00 United Kingdom; ALEXANDRA M. Z. SLAWIN, EaStCHEM School of Chemistry, University of St.Andrews, THE SCIENCE AND HUMANITY OF WILLIAM KLEMPERER, THE EARLY YEARS St. Andrews, United Kingdom; HONGHAO WANG, ADAM M DALY, Department of Chemistry and Biochem- istry, University of Arizona, Tucson, AZ, USA; CHARLOTTE CARDINAUD, EaStCHEM School of Chemistry, STEWART E. NOVICK, Department of Chemistry, Wesleyan University, Middletown, CT, USA. University of St.Andrews, St. Andrews, United Kingdom.

William Klemperer was one of the most important and creative experimental physical chemists of the second half of the An efficient synthesis of formamidinium formate is described. The experimental x-ray structure shows both internal twentieth century. With his invention of Molecular Beam Electric Resonance (MBER) spectroscopy coupled with supersonic and external H-bonding to surrounding molecules. However, in the gas phase, this compound occurs as a doubly hydrogen expansion and a “universal detector”, the era of high resolution rotational spectroscopy of weakly-bound van der Waals and bonded dimer. This doubly hydrogen-bonded structure is quite different from the solid state structure. Microwave spectra were hydrogen bonded complexes began in the early 70’s. The speaker was there at the creation. measured in the 6-14 GHz range using a pulsed-beam Fourier transform microwave (MW) spectrometer. The two nonequiv- alent N-atoms exhibit distinct quadrupole coupling. The rotational, centrifugal distortion, and quadrupole coupling con- stants determined from the spectra have the following values: A=5880.05(2), B=2148.7710(2), C=1575.23473(13), 1.5χaa (N1)=1.715(3), 0.5(χbb-χcc) (N1)=-1.333(4), 1.5χaa (N2)=0.381(2), 0.5(χbb-χcc) (N2)= -0.0342(2), and DJ =0.002145(5) 2 MH02 2:03 – 2:18 MHz. The experimental inertial defect, Δ=-0.243amu A˚ , is consistent with a planar structure. Accurate and precise rota- tional constants (A, B and C), obtained from the MW measurements, were closely reproduced, within 1%-2% of the measured THE SCIENCE AND HUMANITY OF WILLIAM KLEMPERER, THE MIDDLE AND LATER YEARS values, with the M11 DFT functional theoretical calculations. Detailed comparison of the measured and calculated A, B, and STEWART E. NOVICK, Department of Chemistry, Wesleyan University, Middletown, CT, USA. C rotational constants confirms the planar doubly hydrogen bonded structure. The calculated nitrogen quadrupole coupling strengths of the monomer are quite different from either of the two nitrogen sites of the dimer. The poor agreement between William Klemperer and his research group, using Molecular Beam Electric Resonance (MBER) spectroscopy, studied a measured and calculated quadrupole coupling strengths shows that the dimer is not locked in the equilibrium structure but is plethora of weakly bound complexes until and beyond his retirement from teaching at Harvard at age seventy-five in 2002. likely undergoing large amplitude vibrational motion of the hydrogen atoms moving between the N and O atoms involved in Many of Klemperer’s research students and postdoctoral associates went on to prolific careers of their own. Bill’s last public the hydrogen bonding. seminar was presented in 2013 and his last publication on weakly bound complexes appeared in 2015 at age eighty-eight.

MH03 2:21 – 2:36 THE APPLICATION OF MOLECULAR ROTATIONAL SPECTROSCOPY TO ANALYZE REGIO- AND STEREOISO- MERS OF CYCLOHEXENE PRODUCED FROM REACTIONS OF A TUNGSTEN BENZENE COMPLEX

REILLY E. SONSTROM, JATE W. BERNARD, UMME H. HOSSAIN, CHRIS A. PEDE, BROOKS PATE, JACOB A. SMITH, W. DEAN HARMAN, Department of Chemistry, The University of Virginia, Charlottesville, MH05 2:57 – 3:12 VA, USA. CHIRALITY ASPECTS IN THE DIMERIZATION OF VICINAL DIOLS

Chemical reactions of transition metal complexes can provide precise stereocontrol of the products. A recent develop- BEPPO HARTWIG,MARTINA.SUHM,Institute of Physical Chemistry, Georg-August-Universitat¨ Gottingen,¨ ment in the Harman lab at the University of Virginia has demonstrated full control of the stereochemistry in the deuteration Gottingen,¨ Germany. of benzene to cyclohexene using a benzene-tungsten metal complex. Complete stereocontrol of the deuteration is important in the development of deuterium substituted active pharmaceutical ingredients that offer improved safety through reduced 1,2-Ethanediol has been shown by FTIR and Raman spectroscopy in supersonic jets to dimerize preferentially in an S4- metabolism. The goal of this project is to quantify any regioisomer and enantiomer impurities in one of the possible reaction symmetric structure with a cyclic pattern of four strained hydrogen bondsa. This forces the two monomers into a heterochiral products, 3-d-cyclohexene, after it has been removed from the metal and functionalized as cyclohexene oxide. Regioisomers OCCO helicity. The equally frequent homochiral encounters lead to a rich variety of nearly isoenergetic, but much less stable can be identified using molecular rotational spectroscopy by simple analysis of the rotational spectrum of cyclohexene oxide. chain topologies with only three hydrogen bonds. The latter had remained elusive in a previous study buta are now identified To validate that quantum chemistry provides a structure of cyclohexene oxide with sufficient accuracy to unambiguously and energetically modulated by chemically freezing the OCCO helicity of the monomers. This is achieved by moving to identify all ten possible singly-deuterated isomers, these regioisomers have been identified in natural abundance in a broad- cyclic diols of different ring sizes. They are explored computationally and in several cases also spectroscopically, exploiting band rotational spectrum (6-18 GHz) and the rotational constants compared to theoretical predictions. The more challenging the established complementarities between Raman and IR spectroscopy for hydrogen bonded systemsb. analysis is the determination of the enantiomeric excess of the deuteration chemistry. The chiral tagging method is proposed a for this analysis and two candidate tag molecules, propylene oxide (PO) and trifluoropropylene oxide (TFPO), have been F. Kollipost, K. E. Otto, M. A. Suhm, Angew. Chem. 2016, 128, 4667. bThomas Forsting, Hannes C. Gottschalk, Beppo Hartwig, Michel Mons, Martin A. Suhm, PCCP, 2017, 19, 10727 evaluated for use in this application. Although chiral tag complexes are formed with both tags, TFPO offers two important advantages over PO. First, the signal levels for the chiral tag complex with TFPO are about a factor of four stronger – a major advantage since there is a limited amount of reaction product for testing (100 mg). Second, tagging with TFPO leads to cooling of the two ring pucker isomers of deuterated cyclohexene oxide and this simplifies the analysis of the enantiomeric composition of the sample. Intermission 54 55

MH06 3:51 – 4:06 MH09 4:45 – 5:00 CHALCOGEN-BONDED TETRAFLUORO-1,3-DITHIETANE WATER COMPLEX: WHAT DOES IT TAKE TO INVERT THE CONFORMATIONAL LANDSCAPE OF PERILLYL ALCOHOL REVEALED BY BROADBAND ROTATIONAL THE WATER? SPECTROSCOPY AND THEORETICAL MODELING

YAN JIN, XIAOLONG LI, QIAN GOU, GANG FENG, School of Chemistry and Chemical Engineering, FAN XIE, NATHAN A. SEIFERT, MATTHIAS HEGER, JAVIX THOMAS, WOLFGANG JAGER,¨ YUNJIE Chongqing University, Chongqing, China; JENS-UWE GRABOW, Institut fur¨ Physikalische Chemie und Elek- XU, Department of Chemistry, University of Alberta, Edmonton, AB, Canada. trochemie, Gottfried-Wilhelm-Leibniz-Universitat,¨ Hannover, Germany; WALTHER CAMINATI, Dep. Chem- istry ’Giacomo Ciamician’, University of Bologna, Bologna, Italy. Perillyl alcohol (PA) is a naturally occurring dietary monoterpene that can be extracted from various plants, such as lavender and peppermint, and its application to human cancer treatment has been explored.1 The rotational spectrum of The rotational spectrum of the water adduct of tetrafluoro-1,3-dithietane has been investigated by using high resolution PA has been investigated using a chirped-pulse Fourier transform microwave (FTMW) spectrometer and a cavity FTMW rotational spectroscopy. Experimental evidence and quantum theoretical analyses revealed that the two moieties are linked to- spectrometer. In parallel, we have carried out extensive conformational searches by scanning relevant dihedral angles and gether through a dominant S-O chalcogen bond. The rotational transitions of four isotopologues are split into two component also using a semi-classical conformational search program, GFN-xTB.2 In total, 108 conformers have been identified and lines due to the internal rotation of the water moiety around its C2 axis. In the HDO isotopologue, a small μc dipole moment confirmed to be true minima with the subsequent DFT calculations. The relative stabilities of the conformers identified and the component is generated which inverts upon water internal rotation, allowing the experimental determination of the tunneling interconversion barriers among them have been explored at the MP2/6-311++G(2d,p) and B3LYP-D3(BJ)/def2-TZVP levels splitting (21.46(5) GHz). Flexible model calculations can reproduce this splitting when the barrier to water internal rotation of theory. Experimentally, 8 conformers have been assigned and the missing low energy conformers have been rationalized in is 87.4(2) cm−1. terms of conformational conversion barriers under a jet expansion condition. A comprehensive study on the conformational distribution of PA may facilitate our understanding of its structural property and possible structural-functional relationship. 1 T. C. Chen, C. O Da Fonseca, A. H Schonthal.¨ Am. J. Cancer Res. 2015, 5, 1580. 2. S. Grimme, C. Bannwarth, P. MH07 4:09 – 4:24 Shushkov, J. Chem. Theo. Comput. 2017, 13, 1989. THE CHALCOGEN-BONDED COMPLEX H3N...S=C=S CHARACTERIZED BY CHIRPED-PULSE BROADBAND MI- CROWAVE SPECTROSCOPY MH10 5:03 – 5:18 EVA GOUGOULA, School of Natural and Environmental Sciences, Newcastle University, Newcastle-upon-Tyne, CHIRAL ANALYSIS OF MOLECULES WITH MULTIPLE CHIRAL CENTERS USING CHIRAL TAG ROTATIONAL UK; CHRIS MEDCRAFT, School of Chemistry, UNSW, Sydney, NSW, Australia;IBONALKORTA,Instituto de SPECTROSCOPY Quimica Medica, IQM-CSIC, Madrid, Spain; NICK WALKER, School of Natural and Environmental Sciences, Newcastle University, Newcastle-upon-Tyne, UK; ANTHONY LEGON, School of Chemistry, University of Bris- REILLY E. SONSTROM, KEVIN J MAYER, CHANNING WEST, BROOKS PATE, Department of Chem- tol, Bristol, United Kingdom. istry, The University of Virginia, Charlottesville, VA, USA; LUCA EVANGELISTI, Dipartimento di Chimica G. Ciamician, Universita` di Bologna, Bologna, Italy. Ground-state rotational spectra were observed for a complex of ammonia and carbon disulphide in the 2.0-18.0 GHz fre- quency range by Chirped Pulse Fourier Transform Microwave Spectroscopy. The complex was generated through supersonic One major challenge in analytical chemistry is the quantitative determination of the ratio of all stereoisomers in a expansion of a dilute mixture of NH3 (1%) and CS2 (1%) in argon. Ten symmetric-top and four asymmetric-top isotoplogues molecule with multiple chiral centers. The analysis is especially challenging if there are no reference samples available for of H3N...CS2 were isolated while using samples either in natural isotopic abundance or with isotopically enriched 15NH3 calibration. In general, a molecule with N chiral centers has 2N stereoisomers. There are 2N-1 distinct structures, the diastere- ... or ND3. The complex has C3v symmetry, with the connectivity of the atoms being H3N S=C=S, thereby establishing that omers, that can be distinguished by traditional rotational spectroscopy. Each diastereomer exists in two non-superimposable the non-covalent interaction is a chalcogen bond involving the non-bonding electron pair of NH3 as the nucleophile and the mirror images – the enantiomers. Menthone is a simple case of a molecule with two asymmetric carbons. The two di- axial region of one of the S atoms of CS2 as the electrophile. It is assumed that the subunit geometries are unchanged upon astereomers are known as menthone and isomenthone and each is chiral. The full analysis of the stereoisomers of several complex formation which is consistent with small values determined for the intermolecular force constant (kσ). A simple commercial samples has been performed using chirped-pulse Fourier transform microwave spectroscopy (CP-FTMW). To model was used to account for the contribution of the subunit angular oscillations to the zero-point motions and thus obtain determine the diastereomer ratio it is necessary to determine all conformers of the molecule with appreciable population in the intermolecular bond length, r(N... S). the pulsed jet sample. The present work expands on previous efforts to assign the lowest conformers of the menthone and isomenthone by analyzing two additional conformers of isomenthone.[1] For a commercial sample where the diastereomer MH08 4:27 – 4:42 ratio was reported in the Certificate of Analysis, we obtained a menthone and isomenthone composition of 82.8+/-0.9 [1] Schmitz, D.; Shubert, V.A.; Betz, T.; Schnell, M., “Exploring the conformational landscape of menthol, menthone, MICROWAVE SPECTRA, MOLECULAR GEOMETRIES AND BARRIERS TO INTERNAL ROTATION IN COM- and isomenthone: a microwave study”, Frontiers in Chemistry 3, 1-13 (2015). [2] Shubert, V.A., Schmitz, D, Schnell, M., PLEXES OF Ar···C5H7N2 AND H2O···C5H7N2 (WHERE C5H7N2 IS 1-, 2-, 4- OR 5-METHYLIMIDAZOLE) “Enantiomer-sensitive spectroscopy and mixture analysis of chiral molecules containing two stereogenic centers – Microwave NICK WALKER, EVA GOUGOULA, School of Natural and Environmental Sciences, Newcastle University, three-wave mixing of menthone”, J. Mol. Spectrosc. 300, 31-36 (2014). Newcastle-upon-Tyne, UK; CHRIS MEDCRAFT, School of Chemistry, UNSW, Sydney, NSW, Australia;JU- LIANE HEITKAMPER,¨ Institute of Physical Chemistry, Karlsruhe Institute of Technology, Karlsruhe, Germany.

Experiments performed to observe the broadband microwave spectra of 1-methylimidazole, 2-methylimidazole, 4- methylimidazole and 5-methylimidazole also yielded the spectra of molecular complexes containing these molecules. The complexes were generated through laser vaporisation of a solid target rod in the presence of a gas sample undergoing super- sonic expansion and containing Ar and H2O precursors. Spectra have thus been recorded for a series of structural isomers of Ar···C5H7N2 and H2O···C5H7N2 where C5H7N2 is an isomer of methylimidazole. Rotational constants, B0, centrifu- gal distortion constants, DJ , and nuclear quadrupole coupling constants, χaa(N) and χbb(N)-χcc(N) have been determined through assignment of the observed rotational spectra. For each of the structural isomers identified, it will be shown that the argon atom of Ar···C5H7N2 coordinates to π electrons of the aromatic ring of methylimidazole. The water molecule in H2O···C5H7N2 binds to the pyridinic nitrogen atom of the methylimidazole sub-unit. For each complex, the barrier to internal rotation, V3, of the methyl group has been determined. 56 57 MI. Large amplitude motions, internal rotation MI03 2:21 – 2:36 Monday, June 17, 2019 – 1:45 PM LESS CONFUSION AND MORE INFORMATION IN NOTATION FOR SYMMETRY GROUPS OF MOLECULES WITH Room: 1024 Chemistry Annex LAMs PETER GRONER, Department of Chemistry, University of Missouri - Kansas City, Kansas City, MO, USA. Chair: Daniel A. Obenchain, DESY, Hamburg, Hamburg, Germany Many molecular symmetry (MS) groups for molecules with periodic large-amplitude motions are semidirect products H ∧F where the invariant subgroup H is a pure permutation group and F is a point group.a Group H is often a direct product of cyclic permutation groups. The point group F is formed by the equivalent rotations and, for starred PI operators, the E∗ b operator. In a modified notation for such MS groups based on the semidirect product decomposition, such as G8 =[4]Cs or G36 = [33]C2v, the numbers within square brackets refer to the cyclic operators in H and the point group symbol refers to F . This has many advantages over just G8 or G36 because (1) it contains the number of periodic internal motions and their periodicities; (2) the symmetry of rotational, vibrational and transition dipole operators are the same as those of the MI01 1:45 – 2:00 point group; (3) this makes it easy to correlate the symmetry labels to those of possible equilibrium structures and vibronic BARRIERS TO INTERNAL ROTATION IN STRUCTURAL ISOMERS OF METHYLIMIDAZOLE DETERMINED BY levels; (4) and to derive qualitative splitting patterns. Each of these advantages is illustrated with examples. The notation BROADBAND ROTATIONAL SPECTROSCOPY can be extended to molecules with coaxial internal rotors on a linear frame. For such molecules with inequivalent rotors, two different valid notations are possible. If the rotors are symmetrically equivalent, the semidirect product corresponds to the EVA GOUGOULA, School of Natural and Environmental Sciences, Newcastle University, Newcastle-upon-Tyne, extended PI (or EMS) group. UK; CHRIS MEDCRAFT, School of Chemistry, UNSW, Sydney, NSW, Australia; JULIANE HEITKAMPER,¨ aC.M. Woodman, Mol. Phys. (1970) 19, 753-780 Institute of Physical Chemistry, Karlsruhe Institute of Technology, Karlsruhe, Germany; NICK WALKER, School bP. Groner, J. Mol. Spectrosc. (2018) 343, 34-43 of Natural and Environmental Sciences, Newcastle University, Newcastle-upon-Tyne, UK.

Imidazoles are a class of aromatic compounds with significant biochemical properties. Some imidazoles are found to be key compounds in cancer growth while functionalizing imidazole in order to synthesize new drugs is a field of increasing interest among medicinal chemists. The ground state rotational spectra of 1-, 2-, 4- and 5-methylimidazole were recorded in the 7.0-18.5 GHz frequency range by Chirped Pulse Fourier Transform Microwave Spectroscopy. Solid samples of 2-, 4-, and 5-methylimidazole were transferred into the gas phase through laser ablation in the presence of argon gas undergoing supersonic expansion. Liquid 1-methylimidazole was placed in a bespoke reservoir which allows direct introduction of the molecule into the flow of argon. Ground state rotational constants, A0,B0,C0, centrifugal distortion constants, DJ ,DJK, MI04 2:39 – 2:54 DK ,d1,d2, and nuclear quadrupole coupling constants, xaa(N), xbb(N)-xcc(N), were determined for all structural isomers of VIBRATION-TORSION-ROTATION INTERACTIONS IN MOLECULES WITH A C3 TOP AND C FRAME: v =3,4 methylimidazole. Detection of 13C and 15N isotopologues in their natural abundance allowed for determination of atomic v s t TORSIONAL AND C–S STRETCHING VIBRATIONAL STATES OF METHYL MERCAPTAN CH3SH coordinates of heavy atoms. V3 barriers to internal rotation of the methyl group were determined and provide an insight into the flexibility of the structural isomers. V. ILYUSHIN, E. A. ALEKSEEV, Radiospectrometry Department, Institute of Radio Astronomy of NASU, Kharkov, Ukraine; YAN BAKHMAT, Quantum Radiophysics Department , V.N. Karazin Kharkiv National Uni- versity, Kharkov, Ukraine; OLENA ZAKHARENKO, HOLGER S. P. MULLER,¨ FRANK LEWEN, STEPHAN SCHLEMMER, I. Physikalisches Institut, Universitat¨ zu Koln,¨ Koln,¨ Germany; SIGURD BAUERECKER, CHRISTOF MAUL, CHRISTIAN SYDOW, Institut fur¨ Physikalische und Theoretische Chemie, Technische Universitat¨ Braunschweig, Braunschweig, Germany; ELENA BEKHTEREVA, Research School of High-Energy Physics, National Research Tomsk Polytechnic University, Tomsk, Russia.

MI02 2:03 – 2:18 We presenta the results of our analysis of the FIR and microwave spectra of the ν8 vibrational state (C-S stretch) of methyl −1 METHYL GROUP INTERNAL ROTATION AND CHLORINE NUCLEAR ELECTRIC QUADRUPOLE COUPLING IN mercaptan CH3SH near 710 cm . The analysis employs a new program which was recently developed for fitting several CHLOROACETONE isolated small-amplitude fundamentals embedded in a pure torsional bath in molecules like methyl mercaptan, in which the frame has Cs symmetry and the methyl top has C3v symmetry. Our study involves the energy levels that belong to the ν8 BRITTANY E. LONG, Department of Chemistry, Trinity University, San Antonio, TX, USA;FRANKEMAR- vibrational state itself as well as to vt = 0, 1, 2, 3, 4 torsional vibrational states of methyl mercaptan. In our analysis we used SHALL, G. S. GRUBBS II, Department of Chemistry, Missouri University of Science and Technology, Rolla, data available in the literature [1,2,3] as well as the results of the new measurements from Kharkiv, Koln,¨ and Braunschweig. MO, USA; S. A. COOKE, Natural and Social Science, Purchase College SUNY, Purchase, NY, USA. In the talk the details of this new study will be discussed. [1] L.-H. Xu, R. M. Lees, G. T. Crabbe, et al., J. Chem. Phys. 137, 104313 (2012). The spectrum of chloroacetone has been recorded using a chirped-pulse Fourier transform microwave spectrometer op- [2] R.M. Lees, Li-Hong Xu, B.E. Billinghurst, J. Mol. Spectrosc. 352, 30-38 (2016). erating between the regions of 6 GHz and 18 GHz. The spectra of the parent, Cl-37, and C-13 isotopologues are visible in [3] R.M. Lees, Li-Hong Xu, B.E. Billinghurst, J. Mol. Spectrosc. 319, 45-56 (2018). natural abundance. Rotational transitions from within each of the A and E torsional sublevels are resolvable and are split due to the chlorine nuclear electric quadrupole. Variables of appropriately formed Hamiltonians have been fitted to the data sets aThis work was done under support of the Volkswagen foundation. The assistance of Science and Technology Center in Ukraine is acknowledged (STCU partner project P686). The work in Koln¨ was supported by the Deutsche Forschungsgemeinschaft (DFG) via SFB 956, project B3, and the Geratezentrum¨ Cologne Terahertz Center. using both a principal axis method, via Herb Pickett’s SPFIT software, and an extended internal axis method, using Holger Hartwig’s XIAM software. Spectroscopic constants will be presented and compared to quantum chemical calculations and also to analogous constants from other halogenated acetones.

Intermission 58 59

MI05 3:33 – 3:48 MI07 4:09 – 4:24 ISOLATED SMALL-AMPLITUDE FUNDAMENTALS EMBEDDED IN A PURE TORSIONAL BATH: FIR AND MW HYDROXYL GROUPS INTERNAL ROTATION IN THE METHANEDIOL MOLECULE. DFT STUDY INCLUDING SPECTRA OF THE ν10 VIBRATIONAL MODE AND HOT TORSIONAL BANDS OF ACETALDEHYDE DISPERSION INTERACTION.

V. ILYUSHIN, E. A. ALEKSEEV, OLGA DOROVSKAYA, Radiospectrometry Department, Institute of Ra- ULADZIMIR SAPESHKA, Physics, University of Illinois at Chicago, Chicago, IL, USA;GEORGEPITSE- dio Astronomy of NASU, Kharkov, Ukraine; MARIIA KALAMBET, Quantum Radiophysics Department , V.N. VICH, Physics, Belarusian State University, Minsk, Belarus;ALEXMALEVICH,Mechanics and Mathematics, Karazin Kharkiv National University, Kharkov, Ukraine; L. MARGULES,` R. A. MOTIYENKO, MANUEL Belarusian State University, Minsk, Belarus; VALERY SATSUNKEVICH, Physics, Belarusian State University, GOUBET, UMR 8523 - PhLAM - Physique des Lasers Atomes et Molecules,´ University of Lille, CNRS, F- Minsk, Belarus. 59000 Lille, France; OLIVIER PIRALI, AILES beamline, Synchrotron SOLEIL, Saint Aubin, France;SIG- URD BAUERECKER, CHRISTOF MAUL, CHRISTIAN SYDOW, Institut fur¨ Physikalische und Theoretische Methanediol (MD) molecule is of considerable interest to the field of astrophysics[1]. Studies present calculations of Chemie, Technische Universitat¨ Braunschweig, Braunschweig, Germany; GEORG CH. MELLAU, Physikalisch the geometry and IR spectrum of the molecule, however, torsional spectra had yet to be computed. This work presents Chemisches Institut, Justus Liebig Universitat Giessen, Giessen, Germany; ISABELLE KLEINER, Laboratoire calculations of 2D PES MD at B3LYP/acc-pVTZ/cc-pVQZ and B3LYP-D3/acc-pVTZ/cc-pVQZ levels. Computations used Interuniversitaire des Systemes` Atmospheriques´ (LISA), CNRS et Universites´ Paris Est et Paris Diderot, Creteil,´ optimized geometries for all structural parameters at each node with set torsion angles. Kinematic parameters were calculated France; JON T. HOUGEN, Sensor Science Division, National Institute of Standards and Technology, Gaithers- using Wilson s vector formalism. Potential energy calculations were performed at nodes of equidistant grids, number of nodes burg, MD, USA. used 15 × 15 and 45 × 45. The energy values of the torsion levels were determined using DVR method. Figure on the right (a) 2D a We present the results of achieved progress in our analysis of the far-IR and microwave spectra of the ν10 vibrational PES for torsion movement of hy- b −1 state of acetaldehyde . The analysis of the gs - ν10 band near 509 cm involves the energy levels that belong to the vt =0, droxyl groups of MD molecule cal- 1 torsional states of ν10 vibrational mode as well as vt =0, 1, 2, 3, 4 torsional states of the ground vibrational state. The culated in the B3LYP-D3 approx- intervibrational interactions between ν10 vibrational state and torsional bath is taken explicitly into account with the help of imation. (b)Torsional spectra of a new program which was recently developed for fitting several isolated small-amplitude fundamentals embedded in a pure MD molecule at the temperatures torsional bath in molecules with Cs frame and C3v top. Obtained results provide significant progress in comparison with the of 300 K (upper spectrum) and 30 −1 previous fitting attempts for gs - ν10 band of acetaldehyde near 509 cm . In the talk the details of the results with emphasis K (lower spectrum). [1] C. Barri- on the remaining fitting problems for the hot torsional bandsc of acetaldehyde will be discussed. entos, P. Redondo, H. Martinez, A. Largo, Astr.J., 784:132 (2014) 1-7 aThis talk is dedicated to the memory of Dr. Jon T. Hougen (who recently passed away) in recognition of his essential contribution to this project. bThis work was done under support of the Volkswagen foundation. The assistance of STCU is acknowledged (partner project P686). cThe authors are indebted to Dr. A.R.W. McKellar for providing raw spectrum data on torsional bands of acetaldehyde from previous study.

MI06 3:51 – 4:06 MI08 4:27 – 4:42 FTIR SYNCHROTRON SPECTROSCOPY OF THE LOWER MODES OF METHYL-D3 MERCAPTAN (CD3SH) – WHERE IS THE C-S STRETCH? CH3 INTERNAL ROTATION IN 9-METHYLANTHRACENE

CRAIG W. BEAMAN, RONALD M. LEES, LI-HONG XU, Department of Physics, University of New MASAAKI BABA, Division of Chemistry, Graduate School of Science, Kyoto University, Kyoto, Japan; Brunswick, Saint John, NB, Canada; BRANT E. BILLINGHURST, EFD, Canadian Light Source Inc., Saska- MASATOSHI MISONO, Applied Physics, Fukuoka University, Fukuoka, Japan; JON T. HOUGEN, Sensor toon, Saskatchewan, Canada. Science Division, National Institute of Standards and Technology, Gaithersburg, MD, USA.

The infrared Fourier transform spectrum of the lower vibrational modes of CD3SH has been recorded in the 400-1200 We observed the rotationally resolved fluorescence excitation spectrum of the S1 ← S0 transition of jet-cooled 9- −1 cm region using synchrotron radiation at the FIR beamline of the Canadian Light Source in Saskatoon. Torsion-rotation methylanthracene. The potential energy curve for CH3 internal rotation is six-fold symmetric. The barrier to rotation (V6)is −1 −1 −1 assignments have been made for a relatively strong parallel band centered at 644 cm and a weaker perpendicular band ∼ 120 cm [2], which is considerably larger than that of toluene ( ∼ 5cm ) [1]. The V6 value is the energy difference −1 centered at 727 cm . Comparison with the spectra for the normal CH3SH species as well as the analogous CD3OH and between two isomers ‘staggered’and‘eclipsed’. The main contribution to V6 is expected to be hyperconjugation, which is −1 3 CH3OH methanol molecules would suggest an obvious association of the 644 cm band with the C-S stretching mode, the π-like interaction between the aromatic π orbital and methyl sp orbital. −1 with the 727 cm mode likely to be the out-of-plane methyl rock. However, a previous vibrational normal mode analysis The final goal of this work is to quantitatively elucidate the vibrational and rotational energy levels for CH3 internal [Byler and Gerasimowicz, J. Mol. Struct. 112 (1984) 207-219] showed strong coupling between the C-S stretch and CSH rotation. It is essential to observe the high-resolution and high-precision electronic spectra and theoretically search the best bending modes. They assign the 644 cm−1 band to the latter, and attribute the C-S stretch instead to a feature at 688 cm−1 effective Hamiltonian to reproduce the experimental results. We are now developing a new laser control system with optical that we find no clear evidence for in our spectrum. For normal CH3SH, the CSH bend is very weak and lies between the frequency comb locked to GPS, and an ab initio method which provides the reliable potential energy curve. strong C-S stretch and CH3-rocking bands. A Gaussian quantum chemistry calculation of the vibrational frequencies and transition moments was carried out, and indeed there is a mode predicted to lie in between our two observed bands with [1] M. Baba, et al., J. Phys. Chem. A 113, 2369 (2009) almost vanishing intensity and a reduced mass and effective force constant corresponding closely to those calculated for the C-S stretch of normal CH3SH. This apparent dramatic extinction of the normally very strong C-S stretching band is quite [2] D. R. Borst and D. W. Pratt, J. Chem. Phys. 113, 3658 (2000) remarkable! 60 61

MI09 4:45 – 5:00 MJ. Instrument/Technique Demonstration VIBRATIONAL SPECIFICITY AND ISOTOPIC DEPENDENCE OF PROTON-TRANSFER DYNAMICS IN ELEC- TRONICALLY EXCITED 6-HYDROXY-2-FORMYLFULVENE Monday, June 17, 2019 – 1:45 PM

LIDOR FOGUEL, ZACHARY VEALEY, PATRICK VACCARO, Department of Chemistry, Yale University, New Haven, CT, USA. Room: 217 Noyes Laboratory

The vibrational specificity and isotopic dependence of hindered proton-transfer dynamics have been explored in the 1 ∗ Chair: Steven Shipman, New College of Florida, Sarasota, FL, USA lowest-lying singlet excited state, A˜ B2 (π π), of 6-hydroxy-2-formylfulvene (HFF) and its monodeuterated isotopolog (HFF-d). Both systems have been probed under bulk-gas conditions by employing polarization-resolved degenerate four- wave mixing (DFWM) spectroscopy, where judicious selection of incident and detected polarization geometries served to alleviate spectral complexity and to allow for the quantitative extraction of rotation-tunneling information. The observed >1000-fold decrease in tunneling rate that accompanies the π∗← π electron promotion (transitioning from ultrafast ground- state dynamicsa to near-complete quenching of analogous excited-state behavior) makes HFF a compelling model system for investigating the nuanced nature of low-barrier hydrogen bonding and its ability to regulate attendant hydron-migration 1 events. A thorough analysis of low-energy vibronic bands in the A˜ B2 manifold will be presented, with the dependence of uni- molecular reactivity on heavy atom motion and isotopic modification being discussed in the context of structural predictions emerging from high-level quantum-chemical calculations.

aZ. N. Vealey, L. Foguel and P. H. Vaccaro, J. Phys. Chem. Lett. 9, 4949 (2018)

MJ01 1:45 – 2:00 NANOPHOTONIC SUPERCONTINUUM-BASED MID-INFRARED DUAL-COMB SPECTROSCOPY

R. HOLZWARTH, WOLFGANG HANSEL,¨ , Menlo Systems, GmbH, Martinsried, Germany; HAIRUN GUO, WENLE WENG, JUNQIU LIU, SB-IPHYS-LPQM, Ecole´ polytechnique fed´ erale´ de Lausanne, Lausanne, Switzerland; FAN YANG, GFO, Ecole´ polytechnique fed´ erale´ de Lausanne, Lausanne, Switzerland;CAMILLE- SOPHIE BRES,` PHOSL, Ecole´ polytechnique fed´ erale´ de Lausanne, Lausanne, Switzerland;LUCTHEVENAZ,´ GFO, Ecole´ polytechnique fed´ erale´ de Lausanne, Lausanne, Switzerland; DAG SCHMIDT, TOBIAS J. KIP- PENBERG, SB-IPHYS-LPQM, Ecole´ polytechnique fed´ erale´ de Lausanne, Lausanne, Switzerland.

An optically stabilized dual-comb system is used to drive a mid-infrared spectroscopy for parallel gas-phase detection in the functional group region from 2800-3600 cm−1. The system comprises two amplified ultra-low noise fiber frequency combs (FC-1500-ULN from Menlo Systems), centered at 1550 nm wavelength, which are spectrally broadened to the mid- IR by two chip-based Si3N4 waveguides. The probe comb passes through a gas-cell containing CH4 (430 ppm), C2H2 (420 ppm), and N2 as a buffer gas and is eventually superimposed with the reference comb on a photodetector. The dual- comb spectrum below reveals the corresponding absorption features, with sufficient resolution to even resolve isotopologues. The present absorption feature of H2O is due to interaction with water vapour during free-space propagation. 62 63

MJ02 2:03 – 2:18 MJ04 2:39 – 2:54 DUAL-COMB UP-CONVERSION DETECTION OF FUNDAMENTAL MOLECULAR TRANSITIONS HIGH-RESOLUTION SPECTROSCOPY OF POLYAROMATIC HYDROCARBONS WITH A SINGLE MODE TI:SAPPHIRE LASER DISCIPLINED BY AN OPTICAL FREQUENCY COMB ZAIJUN CHEN, THEODOR W. HANSCH,¨ NATHALIE PICQUE,´ Laser Spectroscopy Division, Max Planck Institute of Quantum Optics, Garching, Germany. MASATOSHI MISONO, SHO YAMASAKI, Applied Physics, Fukuoka University, Fukuoka, Japan; SHUNJI KASAHARA, Molecular Photoscience Research Center, Kobe University, Kobe, Japan; MASAAKI BABA, We present a new approach to mid-infrared dual-comb spec- Division of Chemistry, Graduate School of Science, Kyoto University, Kyoto, Japan. troscopy. Strong fundamental ro-vibrational transitions are inter- a 1.0 b rogated in the mid-infrared 3-μm region, while the detection is 1 Hz We have been studied the dynamics of polyaromatic hydrocarbons by high-resolution spectroscopy with a supersonic performed in the near-infrared telecommunication region where 0.5 molecular beam. The target molecules are 9-methylanthracene, 1,2-benzanthracene, perylene, and so on. For the rotationally- sensitive opto-electronic tools are available. Using difference- -100 10 resolved spectra of these molecules, the determination of the frequency axis is a crucial issue [1]. frequency detuning (Hz) frequency generation, a near-infrared comb is converted to the Intensity (a.u.) 0.0 In this study, we developed a frequency control system of a CW Ti:Sapphire laser disciplined by an Er-doped fiber range of 2700-3400 cm−1, where it interacts with the sample optical frequency comb. The frequency of the Ti:Sapphire laser is scanned over several GHz with the uncertainty of about 15 before being converted back to the telecommunication region. 3000 3020 3040 3060 kHz. Or the Ti:Sapphire laser frequency is fixed to an arbitrary single value for a long time interval. Now we try to observe wavenumber (cm-1) There, it beats with a second comb of slightly different line c 1.0 high-resolution spectra of polyaromatic hydrocarbons with this system. spacing for multiheterodyne detection. The broadband spectra [1] A. Nishiyama, A. Matsuba, and M. Misono, Opt. Lett. 39, 4923 (2014). obtained within arbitrarily long averaging time show resolved 0.5 comb lines, a frequency scale calibrated within the accuracy of

an atomic clock and a negligible contribution of the instrument Intensity (a.u.) 0.0 line shape, as in previous reports using our recent scheme of feed- 3016.5 3017.0 3017.5 3018.0 3018.5 a,b forward stabilization . A spectrum (Fig. a, expanded view on wavenumber (cm-1) MJ05 2:57 – 3:12 a single comb line on the radio-frequency scale in Fig.b) in the ULTRAFAST 2D SPECTROSCOPY WITH FREQUENCY COMBS: TOWARDS CAVITY-ENHANCED MULTIDIMEN- 12 region of the Q -branch of the ν3 band of CH4, is measured within 1000 s. The molecular profiles are sampled by the TIONAL SPECTROSCOPY IN MOLECULAR BEAMS comb at a resolution of 3.3 10−3 cm−1(Fig.c) across a total span of 50 cm−1, with an average signal-to-noise ratio of 2540. Comparisons with direct mid-infrared detection will be discussed. PARASHU R NYAUPANE, Department of Chemistry, University of Georgia, Athens, GA, USA; WALKER MANLEY JONES, Chemistry, University of Georgia, Athens, GA, USA; MELANIE A.R. REBER, Department a Z. Chen, M. Yan, T. W. Hansch,¨ and N. Picque,´ A phase-stable dual-comb interferometer, Nat Commun 9, 3035 (2018). of Chemistry, University of Georgia, Athens, GA, USA. bZ. Chen, T. W. Hansch,¨ and N. Picque,´ Mid-infrared feed-forward dual-comb spectroscopy, Proc Natl Acad Sci USA 116, 3454-3459 (2019). Multidimensional spectroscopy has been shown to be a powerful tool to study dynamics of complex systems in the condensed phase. However, 2D spectroscopy in the gas phase, specifically of dilute species in molecular beams, has yet to be realized. There are many complex systems, such as small clusters or transient intermediates, for which the added information from 2D spectroscopy would aid in the understanding of structures and dynamics. We use the unique properties of frequency comb lasers to improve multidimensional spectroscopy with the goal of ultrafast, 2D-spectroscopy of dilute species in molecular beams. First, we are creating a novel 2D spectrometer utilizing a homebuilt Yb-fiber frequency comb MJ03 2:21 – 2:36 laser and an electro-optic modulator-based frequency comb. Inspired by dual-comb spectroscopy, this converts the signal FREQUENCY COMB PHASE-LOCKED CAVITY RING-DOWN SPECTROSCOPY from optical to radio frequencies via heterodyne detection and eliminates the need for a traditional spectrometer. A second benefit of using frequency comb lasers is that the ultrafast pulses can be coupled into enhancement cavities, greatly increasing ZACHARY REED, JOSEPH T. HODGES, Material Measurement Laboratory, National Institute of Standards the sensitivity of the technique. By improving the sensitivity, ultrafast 2D spectroscopy of dilute species in molecular beams and Technology, Gaithersburg, MD, USA. will be possible for the first time. Current progress towards cavity-enhanced 2D spectroscopy will be discussed. Cavity ring-down spectroscopy (CRDS) is a widely used tool for trace gas sensing and molecular lineshape studies which involves the use of high-finesse optical cavities to provide long effective pathlengths and high spectral resolution. Here, we present a novel implementation of CRDS where the probe laser is phase locked to a self-referenced octave-spanning optical frequency comb referenced to a Cs clock, and in which the optical cavity is subsequently locked to the stabilized probe laser MJ06 3:15 – 3:30 beam. This approach provides an absolute frequency axis and increased coupling efficiency. It allows for frequency steps of AN ECHELON-BASED SINGLE SHOT OPTICAL AND TERAHERTZ KERR EFFECT SPECTROMETER arbitrary size to be made, which can be as small as the order of the linewidth of the stabilized probe laser. The optical cavity follows tunable optical sidebands of the probe laser generated with an electro-optic modulator. This allows for up to 40 GHz GRIFFIN MEAD, GEOFFREY BLAKE, Division of Chemistry and Chemical Engineering, California Institute of tuning in a single spectral scan, with spectral intervals as small as 200 kHz. The optical cavity is locked to the stabilized of Technology, Pasadena, CA, USA. probe laser by inducing a slight axial dither (20 kHz modulation amplitude in the optical domain) on a piezo-driven cavity mirror. The resulting transmitted probe beam generates an error signal which can be used to center the piezo offset voltage The design and performance characteristics of an echelon-based single shot visible/near-infrared/far-infrared spectrom- with a low-bandwidth lock. The absolute frequency uncertainty of the locked probe laser is 1 kHz on a timescale of several eter are presented. The spectrometer can measure both the nonlinear optical and terahertz Kerr effects in neat molecular hours, which is well in excess of the measurement time. We present a variety of measurements that highlight the power of liquids. Tens of picoseconds of molecular information can be recorded at a time, with adequate sensitivity to measure molec- this technique. Line positions and pressure shifting coefficients can be determined with nearly an order of magnitude smaller ular responses in just a few milliseconds of experimental time. The signal-to-noise performance was found to scale favorably uncertainty by comparison to those obtained using conventional FS-CRDS measurements. We apply this technique to several with respect to the standard stage scan technique. These results demonstrate the viability of stage-free nonlinear Kerr effect H2OandCO2 transitions in the 1.6 μm wavelength region and report standard uncertainties in line positions as low as 20 measurements and provide a route for improvements to the speed of future multidimensional Kerr effect studies. kHz.

Intermission 64 65

MJ07 4:09 – 4:24 MJ09 4:45 – 5:00 2-CEME AND NOT 2-CEME: MULTI-PULSE TECHNIQUES AS APPLIED TO THE ROTATIONAL SPECTRA OF 2- PROGRESS AROUND THE HIGH RESOLUTION HETERODYNE SPECTROMETER OF THE AILES BEAMLINE CHLOROETHYL METHYL ETHER AND 1,2-EPOXYBUTANE OLIVIER PIRALI, AILES beamline, Synchrotron SOLEIL, Saint Aubin, France; ZACHARY BUCHANAN, De- ERIKA RIFFE, ERIKA JOHNSON, STEVEN SHIPMAN, Department of Chemistry, New College of Florida, partment of Chemistry, The University of California, Davis, CA, USA; SOPHIE ELIET, JOAN TURUT, In- Sarasota, FL, USA. stitut d’Electronique de Microelectronique´ et de Nanotechnologie, Universite´ de Lille 1, Villeneuve d’Ascq, France; MARIE-ALINE MARTIN-DRUMEL, CNRS, Institut des Sciences Moleculaires d’Orsay, Orsay, Strong-field coherence breaking (SFCB)a and other multi-pulse techniques provide promise for greatly accelerating the France; FRANCIS HINDLE, ROBIN BOCQUET, Laboratoire de Physico-Chimie de l’Atmosphere,` Univer- rate at which complex spectra can be assigned. Last year, I presented on the use of SFCB for simplifying the spectra of allyl site´ du Littoral Coteˆ d’Opale, Dunkerque, France;P.ROY,AILES beam line, Synchrotron Soleil, Gif-sur-Yvette, chloride.b Now, I present an update to the use of SFCB and other multi-pulse techniques for analysing rotational spectra France; JEAN-FRANC¸ OIS LAMPIN, UMR CNRS 8520, Institut d’Electronique de Microelectronique´ et de Nan- collected at and near room temperature, using the molecules 2-chloroethyl methyl ether (2-CEME) and 1,2-epoxybutane as otechnologie, Villeneuve d’Ascq, France;GAEL¨ MOURET, Laboratoire de Physico-Chimie de l’Atmosphere,` test cases. The use of these techniques and their significance in the simplification of complex spectra will be discussed. Universite´ du Littoral Coteˆ d’Opale, Dunkerque, France.

a A.O Hernandez-Castillo, Chamara Abeysekera, Brian M. Hays, Timothy S. Zwier, “Broadband Multi-Resonant Strong Field Coherence Breaking as a Tool for Single Isomer a Microwave Spectroscopy.” J. Chem. Phys. 145, 114203 (2016). Our consortium is currently developing a new spectrometer on the AILES beamline of the SOLEIL synchrotron facility bRiffe, Erika; Zwier, Timothy S.; Hernandez-Castillo, Alicia O.; Fritz, Sean; Shipman, Steven; Johnson, Erika. “The Conformer Specific Room-Temperature Rotational to achieve sub-MHz resolution in the THz and far-IR regions. This spectrometer is based on heterodyne mixing of the far-IR Spectrum of Allyl Chloride Utilizing Strong Field Coherence Breaking, International Symposium on Molecular Spectroscopy,” 73rd International Symposium on Molecular Spectroscopy, Talk TI11 (2018). synchrotron radiation with various local oscillators (LOs). In past years, we used a frequency multiplication chain to provide LO frequencies which enabled both a deep characterization of the spectral composition of the synchrotron emissionb and the c recording of its first Doppler limited absorption lines (of D2O) . We recently improved our set-up and measured absorption lines using a far-IR molecular laser pumped by a 10 μm QCL as the LO. The principle of the spectrometer, together with the first experimental results, will be presented in the talk.

aANR ”HEROES: HEterodyne Receivers OptimizEd for Synchrotron sources”, Grant number 16-CE30-0020-03 bTammaro, S., Pirali, O., Roy, P., Lampin, J.F., Ducournau, G., Cuisset, A., Hindle, F., Mouret, G. ”High density terahertz frequency comb produced by coherent synchrotron radiation” Nature Communications, 6, 7733 (2015) ctalk WI02, ISMS 2018

MJ10 5:03 – 5:18 BUILDING A DATABASE FOR QCL PUMPED FAR-IR LASERS

ZACHARY BUCHANAN, Department of Chemistry, The University of California, Davis, CA, USA;MARIE- ALINE MARTIN-DRUMEL, CNRS, Institut des Sciences Moleculaires d’Orsay, Orsay, France;SOPHIE ELIET, JOAN TURUT, Institut d’Electronique de Microelectronique´ et de Nanotechnologie, Universitede´ Lille 1, Villeneuve d’Ascq, France;GAEL¨ MOURET, FRANCIS HINDLE, Laboratoire de Physico-Chimie de l’Atmosphere,` Universite´ du Littoral Coteˆ d’Opale, Dunkerque, France; JEAN-FRANC¸ OIS LAMPIN, UMR MJ08 4:27 – 4:42 CNRS 8520, Institut d’Electronique de Microelectronique´ et de Nanotechnologie, Villeneuve d’Ascq, France; MEASURING BROADBAND TWO-PHOTON ABSORPTION SPECTRA WITH ACCURATE ABSOLUTE CROSS- OLIVIER PIRALI, Institut des Sciences Moleculaires´ d’Orsay, Universite´ Paris-Sud, Orsay, France. SECTIONS IN SOLUTION Our collaborative team is developing new experimental set-ups based on heterodyne mixing of synchrotron radiation CHRISTOPHER G. ELLES, Department of Chemistry, University of Kansas, Lawrence, KS, USA; (extracted by the AILES beamline of SOLEIL) with various Local Oscillators (LOs). In the sub-millimeter and THz regions DAVID A. STIERWALT, Chemistry, University of Kansas, Lawrence, KS, USA. (defined as 0.1–1 THz), LOs from electronic techniques are easy to implement through the use of multiplication chains. However, it is more challenging to produce fixed LOs in the far-IR domain (1–6 THz). The recent development of a new Two-photon absorption (2PA) spectroscopy measures the simultaneous absorption of two photons, where the combined generation of molecular lasers pumped by 10 μmQCLsa allows us to generate many more far-IR frequencies than the previous energy of the two photons corresponds to an allowed transition of a molecule. 2PA is a powerful spectroscopic tool that approach which used CO2 lasers as a pump source. The difficulty in this technique stems from selecting the proper far-IR can probe the electronic structure of a molecule by accessing different electronic states, than in one-photon absorption (1PA) transitions that both involve rotational states susceptible to lase and that are accessible with our 10 μm QCL source. We spectroscopy because 1PA and 2PA are governed by different selection rules. Many applications rely on nonlinear two- will present our program making use of HITRAN, JPL, CDMS, and ExoMol databases to produce lists of far-IR lasing photon excitation, including 3D fluorescence imaging and photo-dynamic therapy; however, broadband 2PA spectra and frequencies. accurate absolute cross-sections are rarely reported in the literature. Our broadband 2PA measurements use a femtosecond a pump-probe technique that is uniquely able to fill this need by measuring continuous 2PA spectra and accurate absolute 2PA Pagies et al., APL Photonics 1 (2016) cross-sections using stimulated Raman scattering (SRS) as an internal standard. Our broadband 2PA technique also recovers additional information based on the relative polarization between the two photons, giving insight into the symmetry of the excited electronic states of a molecule.We report 2PA spectra for coumarin 153 in several solvents, for Mn and Re coordination compounds and for pure liquid benzene. 66 67 MK. Theory and Computation Monday, June 17, 2019 – 1:45 PM MK03 2:21 – 2:36 Room: B102 Chemical and Life Sciences CALCULATION AND VISUALIZATION OF THE VIBRONIC EIGENFUNCTIONS OF JAHN-TELLER ACTIVE Chair: Richard Dawes, Missouri University of Science and Technology, Rolla, MO, USA MOLECULES

KETAN SHARMA, TERRY A. MILLER, Department of Chemistry and Biochemistry, The Ohio State Univer- MK01 1:45 – 2:00 sity, Columbus, OH, USA; JOHN F. STANTON, Physical Chemistry, University of Florida, Gainesville, FL, USA. LOW-LYING ELECTRONIC STATES OF C4H: NOT SIMPLE Jahn Teller active molecules are a convenient tool for understanding various nonadiabatic effects due to a conical in- PAUL DAGDIGIAN, Department of Chemistry, Johns Hopkins University, Baltimore, MD, USA; tersection in the potential energy surface (PES), whether its position is determined by symmetry or accidentally along a JOHN F. STANTON, Quantum Theory Project, University of Florida, Gainesville, FL, USA. reaction path. Computing PES, including the nonadiabatic coupling parameters, helps us to interpret the vibronic spectra of these molecules. Vibronic eigenfunctions are calculable either by utilizing fit data obtained from these vibronic spectra or The C4H molecule is of significant astronomical interest. It represents one of the smallest “carbon chain” radicals, is − electronic structure methods. In this talk we discuss the application and efficacy of these eigenvectors for calculating rovi- abundantly distributed in astronomical sources, and C4H was the one of the first molecular anions to be detected in space. bronic parameters that characterize eigenstates in Jahn-Teller active molecules. Methods have been developed to plot spin The acetylenic radicals H(C2)n form an interesting sequence in which low-lying excited electronic states are conspicuous. 2 2 vibronic eigenfunctions for multimode calculations. These plots give us considerable insight and enhance our understanding The simplest radical (C2H) has a Σ ground state, with the Π excited state just below 0.5 eV higher. As the length of the carbon chain increases, the delocalization present in the 2Π state (relative to 2Σ, which is acetylenic in nature with the by visualizing Jahn-Teller interactions, multimode effects, and potentially the dynamics around a conical intersection. unpaired spin localized on the terminal carbon) leads to its preferential stabilization, and 2Π lies comfortably below 2Σ for C6H and larger members of the series. In this regard, C4H sits essentially on the frontier: the most recent experiments place the 2Σ lowest, but by only <30 meV, and a clear picture of its low-level vibronic level structure has yet to emerge. This talk discusses all three of the low-lying states (2Σ and the two components of 2Π), which in fact display a low-lying MK04 2:39 – 2:54 three-state conical intersection within 150 meV of the minimum on the adiabatic surface, and undergo profound vibronic UNITARY GROUP APPROACH FOR EFFECTIVE POTENTIALS IN 2D SYSTEMS: APPLICATION TO CARBON SUB- 2 2 2 pseudo-Jahn-Teller ( Σ/ Π) and Renner-Teller ( Π) mixing. High-level calculations are performed to identify the various OXIDE C3O2 principal stationary points and conical intersections on the potential, and this information is used to construct a three-state vibronic Hamiltonian of the Koppel-Cederbaum-Domcke¨ variety. These results are used to present a view of the electronic MARISOL RODRIGUEZ´ ARCOS, RENATO LEMUS, Estructura de la Materia, Instituto de ciencias Nucle- structure of this molecule that goes beyond the simple description of simple 2Σ and Renner-Teller distorted 2Π states that has ares, Mexico City, Mexico. typically been invoked in the past, and to carry out a simulation of the photoelectron spectrum. A U(3) algebraic approach is proposed to describe 2D systems for effective potentials. Our approach is based on the 2D vibron model where the addition of a scalar boson is introduced into the 2D harmonic oscillator space. As a crucial ingredient of our approach an algebraic realization of the coordinates and momenta is obtained. This feature provides the tools to MK02 2:03 – 2:18 obtain the algebraic representation of a 2D Hamiltonian in terms of similitude transformation of a diagonal matrix. As an application of our approach the rotation-bending energy levels of carbon suboxide C3O2 are described in good agreement DELTA-COUPLED-CLUSTER METHODS FOR ACCURATE CALCULATIONS OF CORE IONIZATION ENERGIES with experimental data [1]. XUECHEN ZHENG, LAN CHENG, Department of Chemistry, Johns Hopkins University, Baltimore, MD, USA. [1] M. Rodriguez-Arcos, R. Lemus, Chem. Phys. Lett., 713 (2018) 266–271 While scalar-relativistic core-valence separated equation-of-motion coupled-cluster [1] methods can provide quantitative description of core ionization energies [2,3], the necessity of including higher excitations (full triples and quadruples) limits the applicability to small molecules. Here we explore the use of delta-coupled-cluster (ΔCC) methods as an efficient alter- native that is applicable to larger molecules. The ΔCC methods perform CC calculations separately for the neutral and core MK05 2:57 – 3:12 ionized states and thus fully account for the orbital relaxation induced by the core hole in the core ionized state. The conver- UNITARY GROUP APPROACH FOR EFFECTIVE POTENTIALS IN 3D SYSTEMS gence difficulty in ΔCC equations [4] is solved by adapting the generic idea of core-valence separation (CVS) [5] to ΔCC. In benchmark calculations of chemical shifts for the core ionization energies for second-row elements, ΔCCSD(T) is shown RENATO LEMUS, MARISOL RODRIGUEZ´ ARCOS, Estructura de la Materia, Instituto de ciencias Nucle- to be as accurate as EOM-CCSDTQ, which is by far a more expensive method. It is also shown that the errors introduced ares, Mexico City, Mexico. by CVS within ΔCC for the absolute values of core ionization energies is around 0.5 eV and should be taken care of when aming at high-accuracy calculations of the absolute values. An algebraic approach based on the unitary U(4) algebra is proposed to describe 3D systems for effective potentials. Our approach is based on the 3D vibron model where the addition of a scalar boson is introduced into the space of a 3D harmonic oscillator keeping constant the total number of bosons N. However instead of dealing directly with the dynamical References symmetries we proceed to identify the coordinates and momenta in the algebraic space. Our approach is based on the mapping between the U(4) ⊃ U(3) ⊃ O(3) dynamical symmetry and the harmonic oscillator states. A minimization procedure is [1] S. Coriani, and H. Koch, J. Chem. Phys. 143, 181103 (2015). used in order to determine the coefficients involved in the algebraic expansion of the coordinates and momenta. This allows [2] R. H. Myhre, T. J. A. Wolf, L. Cheng, S. Nandi, S. Coriani, M. Guhr¨ and H. Koch, J. Chem. Phys. 148, 064106 the kets associated with the different subgroup chains to be linked to energy, coordinate and momentum representations. This (2018). identification provides useful tools to obtain the matrix representation of 3D Hamiltonians in a simple form through the use of the transformation brackets connecting the different bases. The exact energy and wave functions are obtained in the N large [3] J. Liu, D. Matthews, S. Coriani, and L. Cheng, J. Chem. Theory Comp. (2019). DOI:10.1021/acs.jctc.8b01160. limit. As an application of this approach the eigensystem of the 3D-Morse potential is analyzed, whose wave functions are contrasted with the approximate analytical solutions for null angular momentum. The analyses of inertia moments as well as [4] N. A. Besley, Chem. Phys. Lett. 542, 42 (2012). the dipole moment strengths are also included. This approach provides results which contrasts to the 3D-vibron model where [5] L. S. Cederbaum, W. Domcke, J. Schirmer, and W. von Niessen, Phys. Scripta 21, 481 (1980). the Morse functions are identified with a dynamical symmetry. 68 69

MK06 3:15 – 3:30 MK08 4:27 – 4:42 UNCERTAINTIES IN COMPUTER SPECTROSCOPY FROM MACHINE LEARNING CALCULATION OF FRANCK CONDON FACTORS FOR METAL-CONTAINING DIATOMIC MOLECULES OF IN- TEREST TO LASER COOLING USING COUPLED-CLUSTER TECHNIQUES NIKESH S. DATTANI, Digital Technologies, National Research Council of Canada, Waterloo, ON, Canada. HANNAH KORSLUND, LAN CHENG, Department of Chemistry, Johns Hopkins University, Baltimore, MD, + Computer spectrometers have recently been used to ‘measure’ the energy associated with the C → C ionizationa,the USA; NIKESH S. DATTANI, Harvard-Smithsonian Center, Harvard University, Boston, MA, USA. (13Σ+) → a (13Σ+)bc Li2 u 2Li separation , and the vibrational levels and vibrational spacings of Li2 u . These were all cases involving up to 6 electrons. Up to at least 6 electrons, computer spectroscopy has been as accurate, almost as accurate, Franck Condon factors (FCFs) among low-lying electronic states of a molecule are of paramount importance in the study or in some cases even more accurate, than the best laboratory spectrometers, for measuring quantities such as ionization of laser cooling based on optical cycles. The accurate calculation of potential energy surfaces for these electronic states is key energies and dissociation energies, but we lag behind laboratory experimentalists when it comes to assigning uncertainties to obtaining accurate FCFs. Multireference configuration interaction as a standard approach for computing potential energy on our ‘measurements’: There is no easy way to do it accurately. Typically basis set incompleteness is the biggest source of surfaces has been the method of choice in many applications. Since the laser cooling procedure focuses on the low-lying uncertainty in computer spectroscopy. Energies are calculated with larger and larger basis sets, and then an extrapolation is vibrational states, only the local potential energy surfaces, for which the multi-reference character is often not pronounced done to approximate a CBS (complete basis set) energy. The uncertainty associated with this approximation can be estimated and it is the treatment of dynamic correlation that determines the accuracy of the calculation, are relevant. Therefore, we based on doing multiple extrapolations, with slightly different models, and looking at the spread of extrapolated values, but advocate the use of coupled-cluster (CC) techniques, which provide systematic treatments of dynamic electron correlation, this is still a rather ad hoc way to estimate the uncertainty. Similar extrapolation schemes are also starting to become popular to obtain accurate computational results for FCFs. The yttrium oxide molecule that is subject to active experimental studies for estimating the correlation energy at a given basis set size. [1-3] is adopted here as an example to demonstrate the accuracy of the FCFs using CC potential energy surfaces. My proposal is to develop a way to assign uncertainties to computer spectroscopy measurements in a way more similar to how it is done for laboratory instruments. Instruments often have a ‘precision rating’ based on the likelihood that the true value of the measured quantity is outside a specified window of precision around the number reported by the instrument. The References measurement uncertainties reported in NIST’s atomic spectra database are 1σ uncertainties, meaning that there is approxi- mately a 1/3 chance of the true value being outside of the reported error bar. The precision rating can therefore be calibrated [1] M. T. Hummon, M. Yeo, B. K. Stuhl, A. L. Collopy, Y. Xia, and J. Ye, Phys. Rev. Lett. 110, 143001 (2013). by doing many measurements, but for computer spectrometers we rely on building a big database and doing machine learning. [2] A. L. Collopy, M. T. Hummon, M. Yeo, B. Yan, J. Ye, New J. Phys. 17, 055008 (2015). I discuss the determination of uncertainties both for CBS extrapolations and for FCI energy estimations.

a −1 −1 + [3] A. L. Collopy, S. Ding, Y. Wu, lan A. Finneran, L. Anderegg, B. L. Augenbraun, J. M. Doyle, and J. Ye, Phys. Nike Dattani (2018) “0.06 cm Discrepancy for Li2 → 2Li and 0.994 cm for C → C between Laboratory and Computer Spectrometers” Proceedings of the 73rd International Symposium on Molecular Spectroscopy. Rev. Lett. 121, 213201 (2018). bNike Dattani (2017) “Computer Spectrometers”. Proceedings of the 72nd International Symposium on Molecular Spectroscopy. c − Nike Dattani, Sandeep Sharma, Ali Alavi (2016) “Full CI Benchmark Potentials for the 6e System Li2 with a CBS Extrapolation from aug-cc-pCV5Z and aug-cc-pCV6Z Basis Sets Using FCIQMC and DMRG”. Proceedings of the 71st International Symposium on Molecular Spectroscopy. MK09 4:45 – 5:00 UNDERSTANDING SOLVENT EFFECT ON THE FLUORESCENCE SPECTRA OF 4-VINYL-N,N-DI(P- TOYLY)ANILINE DERIVATIVES

THOMAS T TESTOFF, Department of Chemistry and Biochemistry, Southern Illinois University, Carbondale, IL, USA; LICHANG WANG, Department of Chemistry and Biochemistry, Southern Illinois University Carbon- Intermission dale, Carbondale, IL, USA. DFT calculations were carried out to obtain the absorption and fluorescence spectra of 4-vinyl-N,N-di(p-toyly)aniline derivatives denoted as MTPAs, in different solvents to understand the correlation between the functional groups and solvent effects. In this presentation, we will discuss DFT results on six MTPAs in two solvents, dichloromethane and toluene, and MK07 4:09 – 4:24 the solvent impact on the structures of electronically excited states. We will also briefly discuss the choice of functional of FIRST-PRINCIPLES STUDY OF INFRARED AND RAMAN SPECTRA OF INTERMEDIATES IN ETHANOL CON- the DFT results with comparison to the experimental measurements of these derivatives. VERSION TO ETHYL ACETATE AND HYDROGEN MK10 5:03 – 5:18 RUITAO WU, LICHANG WANG, Department of Chemistry and Biochemistry, Southern Illinois University Car- SIMULATING THE THZ-THZ-RAMAN SPECTRUM OF MOLECULES. APPLICATION TO BROMOFORM. bondale, Carbondale, IL, USA. IOAN-BOGDAN MAGDAU, Chemistry and Chemical Engineering, California Institute of Technology, Ethanol dehydrogenation dimerization to form ethyl acetate (EA) and hydrogen is, in principle, the best atomically Pasadena, CA, USA; GEOFFREY BLAKE, THOMAS F. MILLER III, Division of Chemistry and Chemical economic reaction and is also considered to be an environmentallly friendly process in EA synthesis. Even though the Engineering, California Institute of Technology, Pasadena, CA, USA. copper-based catalysts have been utilized as commercial catalysts they still have some disadvantages such as low productivity and difficult separation from the by-products. Density functional theory was used to investigate the ethanol dehydrogenation Recently developed two dimensional THz-THz-Raman (TTR) spectroscopy applied to liquids is an excellent tool for dimerization over Cu(111) catalyst. In this work, we calculated and analysed the reaction network on Cu(111) along different probing dynamics which takes place at room temperature and drives processes such as solvation, protein folding, and ion dehydrogenation pathways. In addition, to improve the performance of Cu-based catalyst, we investigated the activities over diffusion. The TTR spectrum packs rich information about the systems under study, such as the degree of anharmonicity Cu3Pt(111) and Cu3Pd(111). By comparsion, the introduction of Pt or Pd is beneficial for the improvement of catalytic and mechanical coupling of the low energy modes, and the nonlinearity of the dipole and polarizability surfaces. However, activity. The analysis of density of eletronic states was used to explain how these electron transfers were proceeded over these properties are difficult to interpret, being convoluted into a three point correlation function. We develop a computational different catalysts. Through calculating the entire frequencies of each intermediate, the Infrared and Raman spectra for each procedure based on Reduced Density Matrix (RDM) dynamics, which allows us to calculate the microscopic properties of a intermediate were predicted that will be useful to experimental detection of intermediates. molecule by fitting to the experimental signal measured in the condensed phase. We apply RDM to liquid bromoform and we obtain parameters of the same order of magnitude with values computed ab initio. This paves the road to a more general protocol that could be extended to other molecules in order to measure and fit electric and mechanical molecular properties. These parameters could further be used to develop more reliable force fields for solvation liquids and biomolecules. 70 71 ML. Vibrational structure/frequencies ML03 2:21 – 2:36 Monday, June 17, 2019 – 1:45 PM HIGH-RESOLUTION MID-IR SPECTROSCOPY OF (E)- AND (Z)-1,3-PENTADIENE USING A QUANTUM CASCADE Room: 2079 Natural History LASER MINH NHAT TRAN, JACOB STEWART, Department of Chemistry, Connecticut College, New London, CT, Chair: Paul Raston, James Madison University, Harrisonburg, VA, USA USA.

Samll conjugated dienes serve as one of the prototypical reactants in the Diels-Alder cyclization reaction commonly used in organic chemistry. These dienes exhibit an interesting conformational landscape where the lowest energy conformer is a trans conformation with a gauche conformer lying 10-15 kJ/mol higher in energy. The gauche conformer has only recently been unambiguously indentified as a non-planar structure in 1,3-butadiene (the simplest diene) by microwave spectroscopy.[1] We are interested in understanding the effect of the addition of functional groups on the conformational energy landscape of dienes. 1,3-pentadiene presents one of the simplest substitutions with the addition of a methyl group at the end of the 1,3- butadiene unit. ML01 1:45 – 2:00 We have measured room temperature high-resolution infrared spectra of both (E)- and (Z)-1,3-pentadiene using an 13 cm−1 C MONO-SUBSTITUTED ISOTOPOLOGUES OF PROPYNE (H3CCCH): INVESTIGATING THE ACETYLENIC CH external cavity quantum cascade laser (EC-QCL) in the range of 970-1010 . These measurements represent the first STRETCH PERTURBATION high-resolution infrared spectra of these molecules reported to date, with individual rovibrational features exhibiting the Doppler-broadened linewidth of about 0.0016 cm−1. Both (E)- and (Z)-pentadiene exhibit a strong C-type rovibrational KIRSTIN D DONEYa, JILA and NIST, University of Colorado, Boulder, CO, USA; DONGFENG ZHAO, Hefei band (due to a C-H wagging motion) in this region with a strong Q-branch. We will present our analysis of the rotational National Laboratory for Physical Science at Microscale, University of Science and Technology of China, Hefei, structure we have observed, which will provide experimental data to verify computational chemistry of these molecules. China; HAROLD LINNARTZ, Leiden Observatory, Sackler Laboratory for Astrophysics, Universiteit Leiden, Leiden, Netherlands. [1] J.H. Baraban, M.-A. Martin-Drumel, et al., Angewandte Chemie, 57, 1821 (2018)

The acetylenic CH stretch (ν1) fundamental band of propyne is known to have a ”double-crossing” type perturbation that shifts the K-subbands out of normal order. To further investigate this perturbation, we present a combined experimental and ab initio study on the jet-cooled high-resolution infrared spectra of the ν1 fundamental band of the three mono-substituted 13 13 12 12 12 13 12 12 12 13 C isotopologues of propyne: CH3 C≡ CH, CH3 C≡ CH, and CH3 C≡ CH. The experimental spectra are recorded using continuous wave cavity ringdown spectroscopy (cw-CRDS), with the isotopologues produced at natural abun- dance in a continuous supersonic expansion of regular propyne diluted in argon and helium. The K = 0 and 1 subbands of ML04 2:39 – 2:54 all three isotopologues are measured near 3330 cm−1.b FIRST HIGH RESOLUTION INFRARED SPECTRA of 1-D1-PROPANE. FIRST ANALYSIS OF THE ν9 A1 TYPE B −1 aPreviously at Universiteit Leiden (Sackler Laboratory for Astrophysics). BAND NEAR 358 cm bK.D. Doney et al., J. Phys. Chem. A 122 (2), 582 (2018) STEPHEN J. DAUNT, ROBERT GRZYWACZ, Department of Physics & Astronomy, The University of Tennessee-Knoxville, Knoxville, TN, USA; COLIN WESTERN, School of Chemistry, University of Bristol, Bris- tol, United Kingdom; WALTER LAFFERTY, Optical Technology Division, National Institute of Standards and Technology, Gaithersburg, MD, USA; JEAN-MARIE FLAUD, LISA, CNRS, Universites´ Paris Est Creteil´ et Paris Diderot, Creteil,´ France; RICHARD HUTCHINGS, Berry & Associates/ICON Isotopes, Dexter, MI, USA; BRANT E. BILLINGHURST, EFD, Canadian Light Source Inc., Saskatoon, Saskatchewan, Canada.

At the last two ISMS meetings we have reported on our ML02 2:03 – 2:18 13 IR studies of various D and C substituted isotopologues of HIGH-RESOLUTION INFRARED SPECTROSCOPY OF A NON-NATIVE FORMIC ACID CONFORMER propane conducted at the Canadian Light Source synchrotron 13 13 (2- C, 1- C, 2,2-D2,2-D1). This year we are reporting on the KIRSTIN D DONEY, JILA and NIST, University of Colorado, Boulder, CO, USA; ANDREW KORTYNA, PRE- study of the ν9 B-type band of 1-D1-Propane. There are only STON G. SCRAPE, JILA, National Institute of Standards and Technology and Univ. of Colorado, Boulder, CO, two reports of the IR spectra of this molecule both published in USA; DAVID NESBITT, Department of Chemistry, JILA CU-NIST, Boulder, CO, USA. 1949. Neither of these studies could reach the far-IR where this band occurs. We will show the complete high resolution survey The OH stretch (ν1) fundamental band of a non-native (cis vs trans) conformer of formic acid (HCOOH) is observed for  cm−1 the first time using high-resolution direct absorption infrared spectroscopy. The cis-formic acid is produced in a supersonic slit of all regions from 4000 to below 300 . This will help to confirm some of the earlier assignments for this molecule. We discharge plasma expansion of a trans-formic acid/H2 mixture in 70:30 Ne:He. In this talk, we present a detailed ro-vibrational analysis of the experimentally observed OH stretch mode, including determination of accurate rotational parameters and  hope to report the first modern experimental determination of the ground state constants since the 1960 MW study of Lide. vibrational band origin. Ab initio calculations (both at CCSD(T) and DFT levels of theory) are carried out to support the   !"!# experimental assignment and to futher explore the isomerization dynamics between the trans and cis conformers. Furthermore, This new work now includes the centrifugal distortion terms observation of both a- and b-type transitions in the experimental spectrum facilitate accurate determination of the direction of  for the ground state as well as constants for the ν9 state.        the transition dipole moment in the body fixed frame.  

Intermission 72 73

ML05 3:33 – 3:48 ML07 4:09 – 4:24 HIGH RESOLUTION ANION PHOTOELECTRON SPECTROSCOPY OF OLIGOTHIOPHENE LOW-LYING EXCITED MULTI-FACETED SPECTROSCOPIC STUDY OF THE STRUCTURAL CHANGES ASSOCIATED WITH ELEC- STATES TRONIC EXCITATION OF METHYL ANTHRANILATE

GLEN K THURSTON, Department of Chemistry, University of Wisconsin-Madison, Madison, WI, USA; KARL N. BLODGETT, DEWEI SUN, JOSHUA L. FISCHER, Department of Chemistry, Purdue University, COLE R SAGAN, ETIENNE GARAND, Department of Chemistry, University of Wisconsin–Madison, Madi- West Lafayette, IN, USA;EDWINSIBERT,Department of Chemistry, University of Wisconsin–Madison, Madi- son, WI, USA. son, WI, USA; TIMOTHY S. ZWIER, Department of Chemistry, Purdue University, West Lafayette, IN, USA.

Thiophenes are one of the most promising polymeric solar cells, as in the last decade, the efficiency of thiophene-based Methyl anthranilate (MA) is the methyl ester of anthranilic acid. We present the jet-cooled Laser Induced Fluorescence polymer cells has increased from 1% to 11.5%.a Their use is limited by several factors, including a lack of understanding (LIF) UV excitation spectrum, ground (S0) and excited state (S1) Fluorescence Dip Infrared (FDIR) spectra, IR-UV Hole- about their charge-transport properties in solar cells. To this end, we used cryogenic slow electron velocity map-imaging burning (IR-UV HB) spectra, and Dispersed Fluorescence (DFL) spectra of the MA monomer and MA-H2O complex. MA (SEVI) to acquire vibrationally-resolved anion photoelectron spectra of a family of thiophenes, increasing in chain length, is a close analog of salicylic acid, a well-studied molecule thought to undergo keto-enol tautomerism involving excited state ... culminating with a 5-mer thiophene chain (quinquethiophene). These spectra yield electron-affinities, T1 energies, and active H-atom transfer. In the MA monomer, the C6 ring formed by the HaNHb O=C hydrogen bond in the ground state un- vibrations in transitions from the anion to the neutral S0 and T1 states. Comparing experimental spectra with electronic dergoes an unusual increase in hydrogen bond strength following electronic excitation to the S1 state. This is evident in the structure calculations gives information about the delocalization of electrons on increasing length thiophene chains. This will spectroscopy in several ways. The LIF excitation and DFL spectra both show long progressions in several modes involving build a model for the accommodation of electrons in polymers of thiophenes. motion of the NH2 and COOMe groups relative to one another. Furthermore, the coupled NH2 symmetric and asymmet- ric stretch fundamentals appear to uncouple upon UV excitation, giving rise to a broadened (8 cm−1 FWHM), nominally aMehmood, U., et al. (2016). ”Review on recent advances in polythiophene based photovoltaic devices.” Renewable and Sustainable Energy Reviews 57: 550-561. −1 −1 “free” N-Ha stretch at 3458 cm and an N-Hb stretch shifted all the way down to ˜2900 cm . FDIR spectra collected in the mid-IR frequency range show the change in hydrogen bond strength from the perspective of the C=O acceptor group, −1 −1 where the stretch fundamental is shifted down from its S0 position at 1721 cm to 1637 cm in S1. Calculations at the B3LYP-D3/def2TZVP level of theory in large measure capture these frequency shifts and give insight into likely explanations for such drastic changes. Similar behavior is observed in the MA-H2O complex, although the extent of the hydrogen bond strengthening in the S1 state is modulated by the HOH interactions with both the NH2 and C=O groups.

ML08 4:27 – 4:42 MODE-MIXING MATRIX AND THE VIBRATIONAL CO-ASSIGNMENT OF THE ROTATIONAL ISOMERS

YURII PANCHENKO, Department of Chemistry, Lomonosov Moscow State University, Moscow, Russia.

The equation defining the elements of the mode-mixing matrix in the theory of the vibrational spectroscopy for the rotational isomers is considered. The example of using this mode-mixing matrix is represented. The application of this matrix for the analysis of the vibrational spectra of the rotational isomers is considered. The example of using this mode-mixing ML06 3:51 – 4:06 matrix to the investigation of the vibrational spectra of the butadiene-1,3 rotational isomers is given. MAPPING THE CONFORMATION SPACE OF α-PROLINE BY MATRIX-ISOLATION IR SPECTROSCOPY COM- BINED WITH NIR LASER INDUCED CONFORMATIONAL CHANGE AND STATE-OF-THE-ART AB INITIO COM- PUTATIONS ML09 4:45 – 5:00 ANITA SCHNEIKER, TAMAS VOROS, GYORGY TARCZAY, Institute of Chemistry, Eotvos University, Bu- COMB-LOCKED CAVITY-ASSISTED DOUBLE RESONANCE SPECTROSCOPY (CLCA-DR) dapest, Hungary; MOHAMED AMIN IBRAHIM, MALGORZATA BICZYSKO, International Centre for Quan- tum and Molecular Structures, Shanghai University, Shanghai, China. JIN WANG, CHANGLE HU, AN-WEN LIU, CUNFENG CHENG, TIAN-PENG HUA, YU ROBERT SUN, YAN TAN, SHUI-MING HU, Hefei National Laboratory for Physical Science at Microscale, University of Sci- The conformers of α-proline were studied by matrix-isolation IR spectroscopy. In order to group the vibrational bands to ence and Technology of China, Hefei, China. different conformers, conformational changes were induced by NIR laser irradiations, by exciting the OH stretching overtone of a selected conformer. For identification, the single conformer spectra were compared to state-of-the-art ab initio computa- Double resonance spectroscopy has been frequently applied in state-selective excitation and to reach energy levels for- tions. Infrared spectra and anharmonic thermodynamic corrections have been computed by means of second order vibrational bidden to single-photon transition. Due to the low cross section of two-photon transitions, usually high-power pulsed lasers perturbation theory (VPT2), with GVPT2 and HDCPT2 models, respectively. A hybrid force-field was developed by addition are needed, which prevent high-precision measurements. Optical resonant cavity can be used to enhance the effective path of the cubic and semi-diagonal quartic B3LYP-D3/SNSD force constants to the (harmonic quadratic) B2PLYP-D3/maug-cc- length and also the laser power inside the cavity. By simultaneously locking two continuous-wave lasers with one high-finesse pVTZ results. As the result of the spectrum analysis, seven conformers could be identified. Four of these conformers were cavity, we established comb-locked cavity-assisted double resonance (CLCA-DR) spectroscopy of molecules. Doppler-free present in the as-deposited matrix, two of them were generated by the NIR laser irradiation, and found to be stable in Ar two-photon CLCA-DR spectroscopy of the monoxide carbon molecule were recorded by using two diode lasers with milli- matrix. The seventh conformer could also be produced upon the NIR laser irradiation, and it decays by H-atom tunneling to watts power in the 1.5μm region. Three different types of double resonance: Λ-, V- and ladder-type, were demonstrated. a lower energy form on the sub-second and minute timescales in Ar and N2 matrices, respectively. By comparison to the energy difference obtained in previous high-precision single-photon spectroscopy using comb-locked cavity ring-down spectroscopy [1], we confirmed that the CLCA-DR measurement can also achieve an accuracy of kHz level. The energy of the highly excited state of 12C16O, V=6, J=9 was determined to be kHz level (δE/E is about 10−11)bya “ladder-type” double resonance measurement using the V=3, J=10 level as the intermediate state. Keywords: cavity assisted; double resonance; Doppler free; Reference: [1] Wang, J. et al., J. Chem. Phys. 2017, 147: 091103. 74 75 TA. Mini-symposium: Astrochemistry and Astrobiology in the age of ALMA ML10 5:03 – 5:18 Tuesday, June 18, 2019 – 8:30 AM ALGEBRAIC APPROACH FOR AN ACCURATE SIMULATION OF CO2 RAMAN SPECTRA Room: 116 Roger Adams Lab Chair: Brian Drouin, California Institute of Technology, Pasadena, CA, USA MARISOL BERMUDEZ´ MONTANA˜ , Chemistry Faculty, National Autonomous National of Mexico, Mexico City, Federal District, Mexico; RENATO LEMUS, Estructura de la Materia, Instituto de ciencias Nucleares, Mexico City, Mexico; MIGUEL CARVAJAL, FRANCISCO CURRO PEREZ-BERNAL,´ Dpto. Fisica Aplicada, Unidad Asociada CSIC, Facultad de Ciencias Experimentales, Universidad de Huelva, Huelva, Spain. TA01 8:30 – 8:45 −1 A SIMULTANEOUS FIT OF v = 0 AND 1 TORSION-WAGGING-ROTATIONAL LEVELS OF METHYLAMINE USING We present an accurate simulation of the Raman spectrum of the carbon dioxide molecule in the 1150–1500 cm spectral t A HYBRID (TUNNELING AND NON-TUNNELING) HAMILTONIAN FORMALISM range, comparing the results obtained using different polyad schemes. We first determine an optimal set of Hamiltonian interactions for the three different polyad schemes to after fit the 178 experimental term energies found in the literature. ISABELLE KLEINER, Laboratoire Interuniversitaire des Systemes` Atmospheriques´ (LISA), CNRS et Univer- Thereafter, using a Taylor series expansion of the mean polarizability in terms of normal mode coordinates, we perform an sites´ Paris Est et Paris Diderot, Creteil,´ France; JON T. HOUGEN, Sensor Science Division, National Institute of additional canonical transformation followed by an anharmonization procedure and a fit to a subset of experimental transition Standards and Technology, Gaithersburg, MD, USA; IWONA GULACZYK, MAREK KREGLEWSKI, Faculty moments. Once these steps are accomplished, the Raman spectrum of CO2 is simulated and compared with the experiment. of Chemistry, Adam Mickiewicz University, Poznan, Poland;R.A.MOTIYENKO,UMR 8523 CNRS - Univer- site´ de Lille, Laboratoire PhLAM, Villeneuve d’Ascq, France; V. ILYUSHIN, Radiospectrometry Department, Institute of Radio Astronomy of NASU, Kharkov, Ukraine.

This work is in memory of Dr. Jon Hougen deceased on January 28th 2019 who dedicated his life to spectroscopy and worked on the present project very actively untill the end of December 2018. We will show the latest results obtained with Jon on the fit of more than 15000 rotational-torsional-wagging transitions in the MW and FIR of vt =0,1ofCH3NH2.Weusedthe recently written hybrid program to fit rotational levels in molecules with one CH3 internal-rotation large-amplitude motion, a one NH2 inversion large-amplitude motion, and symmetry described by the G12 PI group . We will first present an overview of our present best least-squares fit. The data set contains slightly less than 2500 MW and 12754 FIR transitions, which are fit to a weighted standard deviation of 1.13 using 74 parameters. Most of the FIR transitions are taken from recent measurements −1b of the vt = 1-0 band centered near 265 cm , but a number of lines were re-assigned or remeasured. The ground torsional c state (taken mostly from Motyienko et al ) fit within measurement uncertainty but 75 older MW measurements in the vt =1 showed large observed-calculated residuals and were presently discarded from the fit. We believe that our fit, as well as the predictive abilities of the program, are now sufficiently good that we can begin a new measurement campaigns of vt =1MW d data and vt = 2, 3 IR data. This new project will be discussed in the talk .

aJ. T. Hougen and I. Kleiner, J. Phys. Chem. A, 2015, 119, 10664 bI. Gulaczyk, M. Kreglewski, V.-M. Horneman, J. Mol. Spectrosc. 2017,342, 25 cR.A. Motiyenko, V.V. Ilyushin, B.J. Drouin, S. Yu, L. Margules,` Astron.and Astrophys. 2014, 563, A1 dPart of this work has been funded by the Programme National de Physique Chimie du Milieu Interstellaire (PCMI)

TA02 8:48 – 9:03 DETECTING BRANCHING RATIOS OF CHEMICAL REACTIONS AT ASTROPHYSICALLY RELEVANT TEMPER- ATURES USING CHIRPED PULSE MILLIMETER WAVE SPECTROSCOPY IN CONTINUOUS CRESU FLOWS

BRIAN M HAYS, THEO GUILLAUME, THOMAS SANDOW HEARNE, OMAR ABDELKADER KHEDAOUI, ILSA ROSE COOKE, DIVITA GUPTA, SEBASTIEN D. LE PICARD, ROBERT GEORGES, ABDESSAMAD BENIDAR, LUDOVIC BIENNIER, IAN R. SIMS, IPR UMR6251, CNRS - Universite´ Rennes 1, Rennes, France.

The reactions of molecules in interstellar space occur over a wide range of temperatures, down to 10 K or colder. The study of gas-phase chemical reactions at these temperatures has been difficult until the development and implementation of the CRESU (French acronym for Reaction Kinetics in Uniform Supersonic Flow) technique in Rennes. Reaction kinetics at temperatures as low as 6 K has been monitored, but product branching ratios have not yet been measured at such low temper- atures. The recent development of the CPUF (Chirped Pulse in Uniform supersonic Flow) technique has shown that chirped pulse spectroscopy can be combined with uniform supersonic flows, so that the branching ratios of chemical reactions can be examined. This has been extended to the continuous CRESU flows at Rennes, taking advantage of the deep averaging capabil- ities of chirped pulse Fourier transform spectrometers complementing the continuous flows. An E-band chirped pulse Fourier transform spectrometer has been incorporated into a current CRESU instrument to detect reaction products. The effects that the uniform flow has on molecular spectra have been characterized in this frequency range. Reactions of ethylene and cyanide radicals have been monitored using pulsed laser photolysis for product detection. The branching ratios of reactions will be discussed, as well as future directions of the instrument. 76 77

TA03 9:06 – 9:21 TA05 9:42 – 9:57 THE ELECTRICAL DISCHARGE PRODUCTS OF MULTI-COMPONENT MIXTURES PROBED BY BROADBAND O(1D) INSERTION REACTIONS FOR THE FORMATION AND SPECTRAL ANALYSIS OF IMPORTANT INTERSTEL- MILLIMETER-WAVE ROTATIONAL SPECTROSCOPY LAR MOLECULES

BENJAMIN E ARENAS, AMANDA STEBER, FS-SMP, Deutsches Elektronen-Synchrotron (DESY), Hamburg, HAYLEY BUNN, JAY A KROLL, Department of Chemistry, Emory University, Atlanta, GA, USA;CHASEP Germany;SEBASTIEN´ GRUET, UMR 8523 - PhLAM - Physique des Lasers Atomes et Molecules,´ Univer- SCHULTZ, Chemistry Department, Emory University, Atlanta, GA, USA; SAMUEL ZINGA, SUSANNA L. sity of Lille, CNRS, F-59000 Lille, France; MELANIE SCHNELL, FS-SMP, Deutsches Elektronen-Synchrotron WIDICUS WEAVER, Department of Chemistry, Emory University, Atlanta, GA, USA. (DESY), Hamburg, Germany. Insertion of O(1D) into stable precursors has proved an efficient way of producing molecules that are reactive or other- Electrical discharge sources have been used extensively for the generation of molecular ions, radicals, and long chain wise unstable under terrestrial conditions. O(1D) reaction with hydrocarbons occurs preferentially via a barrierless insertion unsaturated hydrocarbons, which have consequently been discovered to be present in the interstellar medium (ISM) [1]. We into C-H bonds. Previously in our lab, O(1D) has been produced via photodissociation of ozone at 248 nm. We have reported have used a discharge source to produce a number of medium-sized, astronomically relevant, neutral organic molecules from successful production of methanol and vinyl alcohol from insertion into methane and ethylene respectivelya, where the excess multi-component mixtures. The discharge products are characterised with our segmented chirped-pulse Fourier transform rotational and vibrational energy was quenched using a supersonic expansion, thereby stabilizing the direct insertion product. millimeter-wave spectrometer, which has been previously applied in our room-temperature studies of cyanides and alcohols Using this technique described by Hays et. al., we aim to produce the important glycine precursor, aminomethanol, via inser- 1 [2]. We will concentrate here on the discharge products of mixtures of molecules already detected in the ISM, such as tion into methylamine. Preliminary results have been obtained using O3 as the precursor for O( D) production, but the side aldehydes in mixture with the nitrogen-containing molecules acetonitrile and ammonia. Any newly-observed species in reactions between O3 and methylamine produce such a wide variety of products that spectral assignment for aminomethanol 1 our spectra can be assigned with rest frequencies and rotational parameters already suitable for interstellar searches with is hampered. We propose to photodissociate N2O using 193 nm light as a source of O( D) production in order to eliminate millimeter-wave radio telescopes, such as the Atacama Large Millimeter/submillimeter Array. Results from our experiments the multitude of side reactions observed with ozone. Here we will present the efforts made towards producing aminomethanol will allow us to better consider reaction pathways towards complex organic molecules in extra-terrestrial environments. and collecting its rotational spectrum in the millimeter/sub-millimeter region. References: [1] M. C. McCarthy et al., Astrophys. J. Suppl. Ser. 129 (2000), 611-623. [2] B.E. Arenas et al., Phys. a Chem. Chem. Phys. 19 (2017), 1751-1756. B. M.Hays, N. Wehres, B. Alligood DePrince, A. A.M. Roy, J. C. Laas, S. L. Widicus Weaver, Chem.Phys. Lett., 630, 18 (2015)

Intermission

TA06 10:36 – 10:51 APPLICATIONS OF H-ATOM QUANTUM-DIFFUSION REACTIONS IN SOLID PARA-HYDROGEN TO ASTRO- CHEMICAL STUDIES: FINDING A MYSTERIOUS LINK BETWEEN INTERSTELLAR ISOCYANIC ACID [HNCO] AND FORMAMIDE [H2NC(O)H]

KAROLINA ANNA HAUPA, Applied Chemistry, National Chiao Tung University, Hsinchu, Taiwan;GYORGY TARCZAY, Institute of Chemistry, Eotvos University, Budapest, Hungary; YUAN-PERN LEE, Applied Chem- istry, National Chiao Tung University, Hsinchu, Taiwan, Institute of Atomic and Molecular Sciences, Academia TA04 9:24 – 9:39 Sinica, Taipei, Taiwan. SPECTRAL ANALYSIS OF A METHYLAMINE AND OZONE MIXTURE Formamide [H2NC(O)H], the smallest molecule containing the biologically important pep- JAYAKROLL, SAMUEL ZINGA, SUSANNA L. WIDICUS WEAVER, Department of Chemistry, Emory Uni- tide bond, was detected in the interstellar medium (ISM) almost 50 years ago. Recent observa- versity, Atlanta, GA, USA. tions have shown that a strong correlation between its abundance and that of isocyanic acid [HNCO] exists in pre- and protostellar environments. It was proposed that this correlation is Aminomethanol is predicted to be present in the interstellar medium (ISM) as a reaction product of radical chemistry in due to effective synthesis of formamide from HNCO by consecutive H-atom addition reactions.a ice mantles on interstellar grains. Aminomethanol is of particular interest as it is a precursor molecule in the reaction predicted However, Nobel et al. showed that bombardment of HNCO ice with H atoms led no formation to form glycine, the simplest amino acid, in the ISM. Under terrestrial conditions, aminomethanol is unstable and thus must of formamide.b So far, no laboratory experiment or theoretical calculations can explain the link- be produced in a supersonic expansion for spectral characterization. Previous work in our lab has used the photolysis of ozone age between these two species. 1 to form electronically excited oxygen atoms, O( D), which insert into a C-H bond in methylamine to form aminomethanol. We utilized the advantages of the solid para-H2 quantum host to investigate the H-atom reactions Analysis of this spectrum, however, has proved difficult due to a significant number of transitions present in the spectrum linking HNCO and formamide. Reactions of H2NC(O)H with H atoms lead to H2NCO, and subsequently HNCO.Fur- as a result of the reaction of ozone with methylamine. We have performed a study collecting the spectra of methylamine ther hydrogenation reactions convert some HNCO back to H2NCO and H2NC(O)H; the reaction with D2NC(O)H clearly and ozone mixtures under dark conditions to determine the reaction products and assign the spectra in order to clarify the showed that these reactions took place. The correlation between the abundance of HNCO and H2NC(O)H can hence be spectral measurements under photolysis conditions. We will report on this analysis, including the assignment of previously understood by a dual-cycle mechanism shown in the figure, which connects the two species by a quasi-equilibrium. This unassigned vibrationally excited states of methylamine up to 1 THz. mechanism and its generalized form for other molecular pairs can also play an important role in the formation of interstellar H2 from H atoms.

aLopez-Sepulcre,` Montly Not. Roy. Astr. Soc. 449, 2438–2458 (2015). bNobel, J. A., et al., Astron. Astrophys. 576, A91 (2015). 78 79

TA07 10:54 – 11:09 TA09 11:30 – 11:45 EXPLOITING TUNABLE VACUUM ULTRAVIOLET PHOTOIONIZATION COMBINED WITH REFLECTRON TIME- PHOTOPHYSICS AND ELECTRONIC STRUCTURE STUDIES OF PROTONATION OF QUINOLINE OF-FLIGHT MASS SPECTROMETRY FOR THE ISOMER-SPECIFIC DETECTION OF COMPLEX ORGANIC MOLECULES FORMED VIA INTERACTION OF IONIZING RADIATION WITH MIXED ASTROPHYSICAL ICE HIRDYESH MISHRA, Department of Physics, Banaras Hindu University, Varanasi, Uttar Pradesh, India. ANALOGUES Study of the photophysics and electronic structure properties of quinoline and its derivatives have been the subject of N. FABIAN KLEIMEIER, MATTHEW JAMES ABPLANALP, Department of Chemistry, University of Hawaii considerable interest because of their commercial and pharmaceutical applications. Some of the quinoline derivatives have at Manoa, Honolulu, HI, USA; REBECCA N. JOHNSON, SAMER GOZEM, Department of Chemistry, Georgia been found as a potential probes for measuring the polarity of microenvironment in chemical and biological systems. Diffuse State University, Atlanta, GA, USA; RALF INGO KAISER, Department of Chemistry, University of Hawaii at interstellar bands in the emission spectrum of the interstellar medium, indicate the presence of quinoline and other small Manoa, Honolulu, HI, USA. polycyclic aromatic nitrogen heterocycles, which readily dissociate under exposure to interstellar radiation. Since the quino- line ring is the basic fluorophor unit in all its derivatives, it is important to understand the change in dynamics and electronic Over 200 molecules have been detected in the interstellar medium (ISM) with close to one third considered to be com- structure of quinoline in presence some external perturbation. Being isoelectronic with naphthalene, these molecules provide plex organic molecules (COMs), molecules containing six or more atoms. Gas-phase reaction networks of ion-molecule useful comparisons for checking the electronic and vibrational state assignments, ionization potentials, and other properties of and neutral-neutral reactions have aided in the understanding of the evolution of the interstellar medium (ISM). However, the parent hydrocarbon. In addition, these molecules possess nonbonding electrons which give rise to n– Pi* states. The loca- these models fail to explain the synthesis of ubiquitous COMs with predicted abundances several orders of magnitude lower tion and characterization of these states are of both theoretical and practical significance. Further, solvents have an important compared to observations in the ISM, such as in Sagittarius B2. Over the last decades astrophysical laboratory simulation ex- influence on the fluorescence property of N-heterocyclic compounds. Experimentally, Quinoline shows vibronic absorption periments have shown that some of these COMs are formed via interaction of ionizing radiation within simple ices deposited spectrum and corresponding large Stoke shifted broad fluorescence emission spectrum having very low quantum yield and 10 NH on interstellar dust particles at K(H2O, CH3OH, CO, CO2,CH4, 3). After processing the ice temperature programmed dual decay time, however protonated quinoline shows red shifted fluorescence spectrum with increase in quantum yield and desorption was utilized to sublime the ice along with its newly formed products for analysis with single photon vacuum ul- fluorescence decay become mono-exponential. To understand the vibronic structure of electronic absorption spectra and pho- traviolet ionization coupled with a reflectron time-of-flight mass spectrometer (PI-ReTOF-MS). The use of PI-ReTOF-MS tophysics of protonation of quinoline, both vibronic and electronic structure studies of quinoline (Q) and protonated quinoline allows for the selective ionization and identification of structural isomers of COMs. Here, we report that the key COMs (QH+) were carried out along with vibrational calculations for absorption and fluorescence bands at B3LYP 6-311++G(d, p) − propynal (HCCCHO) and cyclopropenone (c C3H2O), which have both been detected in the ISM, can be synthesized within level in ground and excited state by density functional methods (DFT) and (time-dependent density functional) TD-DFT 5 interstellar ices containing carbon monoxide (CO) and acetylene (C2H2) at temperatures as low as K. This is accomplished methods respectively with the help of Gaussian 09 software. Normal mode mixing is taken into account by the Duschinsky via non-equilibrium chemistry induced by the energetic electrons simulating those produced by galactic cosmic rays penetrat- transformation. The vibronic structure of strongly dipole-allowed transitions is calculated within the Franck–Condon approx- ing interstellar ices. Furthermore, cyclic COMs may act as tracers for non-equilibrium chemical processes at 10 K involving imation. Weakly dipole-allowed and dipole-forbidden transitions are treated within the Franck–Condon–Herzberg–Teller electronically excited reactants such as acetylene in excited triplet state(s). The incorporation of solid state data from these and Herzberg–Teller approximation, respectively. A good correlation between computational spectroscopic calculations and experiments, such as yield, branching ratio, and chemical and temperature conditions, into astrochemical models accounting experiment results are found to understand the photo-physics of protonation of quinoline. for non-equilibrium has been shown to greatly improve predicted abundances.

TA08 11:12 – 11:27 THE MILLIMETERWAVE SPECTRUM OF SUCCINONITRILE

CARLOS CABEZAS, CELINA BERMUDEZ,´ Instituto de Fisica Fundamental, CSIC, Madrid, Spain;JUAN DANIEL GALLEGO, Centro Astronomico´ de Yebes, Observatorio Astronomico´ Nacional, Yebes, Guadalajara, Spain; ISABEL TANARRO, JOSE´ LUIS DOMENECH,´ VICTOR JOSE HERRERO, Instituto de Estructura de la Materia, (IEM-CSIC), Madrid, Spain;BELEN´ TERCERO, OAN-IGN, Observatorio Astronomico´ Nacional, Madrid, Spain; ROSA LEBRON,´ JESUS´ EDUARDO QUINTANILLA, Instituto Qu´ımica-F´ısica Rocasolano, CSIC, Madrid, Spain; ANA CRISTINA SORIA, Analisis´ Instrumental y Qu´ımica Ambiental, CSIC, Madrid, Spain; JOSE CERNICHARO, Instituto de Fisica Fundamental, CSIC, Madrid, Spain.

Only two dinitriles, the protonated cyanogen NCCNH+ and one isocyanonitrile, NCNC have been detected in the inter- stellar medium (ISM) among about 200 other compounds, despite nitriles constitute almost 20% of the molecules observed in the interstellar medium. The lack of detections of dinitriles may be explained by the lack of accurate spectroscopic data on their rotational spectra since most of them do not present permanent dipole moment. Succinonitrile, NCCH2CH2CN is one of the simplest dinitriles and it could be a candidate molecule to be observed in the ISM. The rotational spectrum for succinonitrile has been previously observed in the 2-78 GHz frequency region by Jahn et al.,a but these measurements were limited to the ground state. In this talk we report the study of succinonitrile and its low lying excited vibrational states using a newly built broadband Fourier transform millimeter wave spectrometer b equipped with Q-band (31.5-50 GHz) and W-band (72-116 GHz) receivers, similar to those used in the radio-telescopes. The spectrometer is well suited for high resolution emission spectroscopy of molecules of astrophysical importance.

aM. K. Jahn, J.-U. Grabow, P. D. Godfrey and D. McNaughton, Phys.Chem.Chem.Phys., 2014, 16, 2100. bJ. Cernicharo et al., A&A, 2019. 80 81 TB. Mini-symposium: Non-covalent Interactions Tuesday, June 18, 2019 – 8:30 AM TB03 9:24 – 9:39 SULFUR HYDROGEN BONDING IN THE OLIGOMERS OF AROMATIC THIOLS Room: 100 Noyes Laboratory RIZALINA TAMA SARAGI, MARCOS JUANES, ALBERTO LESARRI, Departamento de Qu´ımica F´ısica y Chair: Gang Feng, Chongqing University, Chongqing, China Qu´ımica Inorganica,´ Universidad de Valladolid, Valladolid, Spain;JOSEA.FERN´ ANDEZ,´ Departamento de Qu´ımica F´ısica, Universidad del Pa´ıs Vasco (UPV-EHU), Bilbao, Spain.

Following previous experiments on sulfur hydrogen bondinga we have ob- served several oligomers of the aromatic thiols thiophenol, phenylmethanethiol and 2-phenylethanethiol in a jet-cooled expansion using broadband (chirped- pulsed) microwave spectroscopy (2-8 GHz).The homodimers of the three aromatic thiols are primarily stabilized by S-H ··· S hydrogen bonds and other weak interac- TB01 INVITED TALK 8:30 – 9:00 tions. The phenylmethanethiol and 2-phenylethanethiol dimers exhibit additional INTERMOLECULAR NON-COVALENT INTERACTIONS REVEALED BY BROADBAND ROTATIONAL SPEC- combinations of S-H ··· π,C-H··· π or C-H ··· S interactions, while the two phenyl TROSCOPY rings in the thiophenol dimer are stacked, displaying a π-π interaction. A single symmetric-top isomer of the thiophenol trimer has been observed, characterized M. EUGENIA SANZ, Department of Chemistry, King’s College London, London, United Kingdom;S.INDIRA b by a C3 symmetry topologically equivalent to that observed in the phenol and MURUGACHANDRAN, SHEFALI SAXENA, Chemistry, King’s College London, London, UK;ECATERINA anilinec trimers. The trimer structure combines S-H ··· S hydrogen bonds and C- BUREVSCHI, DONATELLA LORU, ISABEL PENA,˜ Department of Chemistry, King’s College London, Lon- H ··· π interactions. Accurate rotational parameters and supporting ab initio and don, United Kingdom; ELENA R. ALONSO, Chemistry, King’s College London, London, UK;JACKSON DFT calculations will be reported at the symposium. TANG, Department of Chemistry, King’s College London, London, United Kingdom. aM. Juanes, A. Lesarri, R. Pinacho, E. Charro, J. E. Rubio, L. Enr´ıquez, M. Jara´ız, Chem. Eur. J., 2018, 24, 6564 Non-covalent interactions play a key role in chemistry, physics and biology, being responsible for the three-dimensional bN. A. Seifert, A. L. Steber, J. L. Neill, C. Perez,´ D. P. Zaleski, B. H. Pate, A. Lesarri, Phys. Chem. Chem. Phys., 2013, 15, 11468 c structure of proteins, the physical properties of condensed phases, and the outcome of molecular recognition processes, to cite C. Perez,´ I. Leon,´ A. Lesarri, B. H. Pate, R. Mart´ınez, Judith Millan,´ J. A. Fernandez,´ Angew. Chem. Int. Ed., 2018, 57, 15112 just a few examples. In this talk we will focus on intermolecular non-covalent interactions and present our results on several complexes investigated by chirped pulsed Fourier transform microwave spectroscopy and computational methods. A range of clusters, involving odorants, aromatic hydrocarbons, alcohols and water will be reviewed. The interplay between primary and secondary hydrogen bonds and/or dispersion forces will be discussed, as well as the performance of several theoretical methods in view of the experimental data.

TB02 9:06 – 9:21 THE MICROWAVE SPECTRUM AND MOLECULAR STRUCTURE OF (E)-1-CHLORO-1,2- DIFLUOROETHYLENE–ACETYLENE TB04 9:42 – 9:57 MICROWAVE SPECTRUM AND INTERNAL ROTATION OF THE THIOACETIC ACID – WATER COMPLEX HELEN O. LEUNG, MARK D. MARSHALL, Chemistry Department, Amherst College, Amherst, MA, USA. ANNA HUFF, CJ SMITH, KENNETH R. LEOPOLD, Chemistry Department, University of Minnesota, Min- The lowest energy structures for haloethylene-protic acid heterodimers result from an interplay between favorable elec- neapolis, MN, USA. trostatic interactions and steric effects. For vinyl fluoride and 1,1-difluoroethylene complexes, steric effects predominate and the resulting planar structure has the acid binding across the double bond (“top”), while for trifluoroethylene, favorable elec- The rotational spectrum of CH3COSH-H2O has been observed by pulsed-nozzle Fourier transform microwave spec- 34 trostatics forces the complexes to adopt a sterically strained, but still planar structure with the acid at one end of the olefin troscopy. Spectra were also recorded for the CH3COSH-D2OandCH3CO SH-H2O isotopologues. A and E internal rotor (“side”). Substitution of a fluorine atom with chlorine allows a relaxation of steric requirements and the side binding motif states were observed for each species and the spectra were fit with the XIAM internal rotation program. Preliminary fits have −1 to chlorine is observed in (Z)-1-chloro-2-fluoroethylene–acetylene despite the presence of the more electronegative fluorine resulted in a methyl internal rotation barrier of V3 = 34.1290(28) cm for the parent CH3COSH-H2O complex, which is −1 atom. Similarly, in 2-chloro-1,1-difluoroethylene ethylene–acetylene, the acetylene prefers to adopt side binding to chlorine in reasonable agreement with the value predicted at the M06-2X/6-311++G(3df,3pd) level of theory (V3 = 43.9 cm ). In −1 despite having the option of top binding to fluorine. In (E)-1-chloro-1,2-difluoroethylene, the possibilities are switched to comparison with the free syn-thioacetic acid monomer (V3 = 76.300(12) cm ), the value of V3 decreased by over half as a top binding to chlorine and side binding to fluorine. Although the side binding arrangement to fluorine is predicted to be result of complexation with water. lower in energy than top binding to chlorine, a non-planar, crossed geometry, with the centers of the HCCH triple bond and ethylene double bond approximately aligned with each other is predicted as the global minimum when not correcting for basis set superposition error. When the correction is made, the non-planar geometry has an energy higher than both side and top binding. The microwave spectra of four isotopologues of the (E)-1-chloro-1,2-difluoroethylene-HCCH complex reveal that the side binding structure is indeed the one with the lowest energy. This structure is discussed in terms of the balance between electrostatics and sterics.

Intermission 82 83

TB05 10:36 – 10:51 TB08 11:30 – 11:45 NON-COVALENT INTERACTIONS IN COMPLEXES OF FLUORINATED AROMATIC RINGS INVESTIGATED BY EXPLORING THE BINDING OF METHANOL WITH FURANS ROTATIONAL SPECTROSCOPY MARIYAM FATIMA, CRISTOBAL PEREZ, DANIEL A. OBENCHAIN, MELANIE SCHNELL, FS-SMP, SONIA MELANDRI, ASSIMO MARIS, LUCA EVANGELISTI, IMANOL USABIAGA, Dipartimento di Deutsches Elektronen-Synchrotron (DESY), Hamburg, Germany. Chimica G. Ciamician, Universita` di Bologna, Bologna, Italy; CAMILLA CALABRESE, Departamento de Qu´ımica F´ısica, Universidad del Pa´ıs Vasco (UPV-EHU), Bilbao, Spain; WEIXING LI, FS-SMP, Deutsches Recently, an infrared study on the complex of dimethylfuran and methanol showed only a slight preference for methanol Elektronen-Synchrotron (DESY), Hamburg, Germany;LAURAB.FAVERO,Istituto per lo Studio dei Materiali to bind via an OH···O hydrogen bond versus the OH···π bond.a From this work, a ‘blind challenge’ was undertaken to Nanostrutturati, Consiglio Nazionale delle Ricerche (ISMN-CNR), Bologna, Italy. compare the quantum chemical and experimental results of the microsolvation of a furan ring in methanol, with varying degrees of methyl substitution on furan, having a focus on methanol binding sites.b The hope of the challenge is to gauge Non-covalent inter- and intramolecular interactions involving aromatic rings are ubiquitous in chemical and biological how well experiment and theory can agree on site preference when the energy difference is near 1 kJ/mol, and ultimately to processes. The presence of halogen atoms, fluorine in particular, can drastically change the binding properties of molecules discern which theoretical models perform the best. and thus halogen or fluorine substitution are used to tune the properties of new materials, drugs or proteins. We report on To this end, we present the rotational spectrum and structural analysis of the dimethylfuran complex with methanol. The a series of rotational spectroscopy studies performed with Molecular Beam Fourier Transform Microwave spectroscopy in rotational spectrum was recorded on the Hamburg COMPACT (compact-passage acquired coherence technique) microwave which we have tested the binding abilities of fluorinated aromatic compounds, namely penta-fluoropyridine and hexafluo- spectrometer from 2−18 GHz.c The observed spectrum is complicated by the internal rotation of three methyl tops, two from robenzene, with different ligands such as ammonia, carbon monoxide and halogenated methanes. The comparison to the the dimethylfuran and one from the methanol. Each methyl top adds additional torsional angular momentum to the rotating analogous complexes formed by non-fluorinated aromatic moieties shows strickingly different structures. In the case of the complex, which subsequently splits the rotational energy levels yielding a complex set of torsion-rotation transitions. The fluorinated aromatic compounds the structures are dominated by π-hole interaction. resulting methyl top tunneling parameters are essential to aid in the structure determination of the complex. These results will be compared with the furan methanol results to see the effect of methylation on site preference.

aA. Poblotzki et al, Phys. Chem. Chem. Phys. 2016, 18, 27265. bH. C. Gottschalk et al, J. Chem. Phys. 2018, 148, 014301. TB06 10:54 – 11:09 cD. Schmitz et al, J. Mol. Spectrosc. 2012, 280, 77. A CONFORMATIONAL STUDY OF THE ALICYCLIC MUSKS ROMANDOLIDE AND HELVETOLIDE USING BROADBAND ROTATIONAL SPECTROSCOPY TB09 11:48 – 12:03 ECATERINA BUREVSCHI, M. EUGENIA SANZ, Department of Chemistry, King’s College London, London, INTERMOLECULAR INTERACTIONS IN AN AZEOTROPE United Kingdom. SNEHA BANERJEE, SOHINI SARKAR, PANKAJ MANDAL, Department of Chemistry, Indian Institute of Musk odorants are important notes in perfumery for their natural, an- Science Education and Research, Pune, Maharshtra, India. imalistic and warm scent. Understanding how structure and odor relate is important for development of new musk classes, with scalable synthesis The structure and dynamics of molecular liquids have been of interest for a long time. Intermolecular interactions, and higher biodegradability. However, musks are generally very flexible especially hydrogen bonding brings about many interesting properties in self-associated liquids. Binary mixtures of molecular and difficult to crystallise, and their conformations are unknown. Here we liquids will have various such interactions that give rise to non-ideality. In some cases, when this non-ideality is large, we present the conformational study of two widely used alicyclic musks, ro- observe the formation of an azeotrope. In this study, we try to understand this non-ideality at a molecular level, using Optical mandolide (C15H26O4) and helvetolide (C17H32O3), using chirped-pulse Kerr Effect (OKE) spectroscopy, broadband (1-10 THz) THz-time domain spectroscopy (THz-TDS) along with temperature Fourier Transform Microwave (CP-FTMW) spectroscopy in combination dependent NMR of the azeotropic as well as other composition mixtures of benzene and methanol. with theoretical methods. Three conformations of romandolide and five Vibrational and NMR spectroscopic studies have shown that the formation of the methanol-benzene azeotrope weak- conformations of helvetolide have been identified in the broadband spec- ens the hydrogen bond network. Intermolecular forces between the benzene molecules have also been reduced significantly. tra of romandolide and helvetolide, respectively. The observed conform- Methanol disrupts the stacking of benzene which is also evident from the depression in the boiling points. With OKE spec- ers adopt horseshoe shapes and are stabilized by dispersion interactions troscopy we can probe both, the collective orientational diffusion and the intermolecular dynamics in liquids. The benzene between the side chain and the cyclohexane ring. spectra show a bimodal character but lack distinct peaks, which is consistent with previous OKE studies a. Simulationsb have shown that while the high-frequency shoulder is attributed purely to rotational motion, the low-frequency mode has contributions from both, the collective translational and the rotational modes. The addition of polar methanol to benzene not only changes the shape of the RSD but also shifts it to lower frequencies. An azeotropic composition mixture was prepared TB07 11:12 – 11:27 at room temperature without further distillation. The spectral densities of this mixture and the azeotrope were quite different THE MICROWAVE SPECTRUM AND MOLECULAR STRUCTURE OF 1-CHLORO-1- from each other, raising the question of this being a temperature driven process. FLUOROETHYLENE–HYDROGEN CHLORIDE Benzene’s entire rotational dynamics show up as molecular reorientation spread throughout the OKE spectra. The centre- of-mass translational part is only visible when it affects the interaction induced (I-I) part of the polarizability. The addition LABONI HOQUE, HELEN O. LEUNG, MARK D. MARSHALL, Chemistry Department, Amherst College, of methanol decreases this contribution of the translations to the I-I term for benzene. A detailed analysis of the RSDs can Amherst, MA, USA. indicate the rate of structural fluctuations in the benzene-methanol mixtures.

aZhong, Q.; Fourkas, J. T. J. Phys. Chem. B 2008, 112, 15529. Recent examples of complexes formed between hydrogen chloride and chlorofluoroethylenes have revealed unexpected bRyu, S.; Stratt, R. M. J. Phys. Chem. B 2004, 108, 6782. and surprising structures. To the contrary, the analysis of the microwave rotational spectrum of 1-chloro-1-fluoroethylene- hydrogen chloride shows that it has the “top binding to fluorine” structure typical of earlier dihaloethylene-HCl complexes. However, this result is not predicted by the MP2/6-311++G(2d, 2p) model chemistry on which we had been relying, even when corrected for basis set superposition error. The success of various model chemistries in predicting the experimental result is discussed. 84 85 TC. Clusters/Complexes Tuesday, June 18, 2019 – 8:30 AM TC03 9:06 – 9:21 USING CONCENTRATION DEPENDENCE OF MICROWAVE SPECTRA OF 2-COMPONENT MIXTURES Room: 1024 Chemistry Annex TO IDENTIFY SINGLE COMPONENT CLUSTERS - APPLICATION TO (FLUOROETHYLENE)n AND (1,1- DIFLUOROETHYLENE)n Chair: Kaori Kobayashi, University of Toyama, Toyama, Japan REBECCA A. PEEBLES, SEAN A. PEEBLES, PRASHANSA KANNANGARA, TULANA ARIYARATNE, Department of Chemistry, Eastern Illinois University, Charleston, IL, USA; BROOKS PATE, CHANNING WEST, Department of Chemistry, The University of Virginia, Charlottesville, VA, USA.

Over the past two years, we have implemented automated analysis of chirped-pulse microwave spectra of two-component mixtures of fluoroethylene (FE) or 1,1-difluoroethylene (DFE) and CO2 to facilitate identification of the numerous cluster a TC01 8:30 – 8:45 spectra present in a single scan. This approach has led to assignment of ten (FE)n(CO2)m clusters and one (DFE)n(CO2)m (FE) MILLIMETER/SUBMILLIMETER DETECTION OF METHANOL CLUSTERS IN A SUPERSONIC EXPANSION cluster, so far. These scans also include spectra of multiple single-component clusters (for instance, n), which were not SOURCE apparent in earlier analyses, since “monomer only” peaks were filtered from data sets during analysis. Present efforts utilize intensity variation amongst two-component scans as a way to identify these single-component clusters. Previously unobserved KEVIN ROENITZ, CONNOR J. WRIGHT, JAY A KROLL, SUSANNA L. WIDICUS WEAVER, Department spectra for five clusters involving only FE or only DFE (and in some cases including neon) have now been assigned. of Chemistry, Emory University, Atlanta, GA, USA. Identifying groups of related transitions and assigning their spectra has proven relatively straightforward, but determining compositions and structures of the carriers of these spectra is challenging. Several approaches, including analysis of the Methanol clusters are a subject of great interest as they give insight into the nature of van der Waals complexes. In concentration dependence of transition intensity and implementation of rapid force-field based structure optimizations, have the course of our experimental study of the protonated formaldehyde ion, we have encountered unknown spectral lines that allowed some progress on determining details of the observed species. are believed to arise from methanol clusters. Both the methanol dimer and methanol-argon clusters have been previously aRebecca A. Peebles, Prashansa B. Kannangara, Sean A. Peebles, Brooks H. Pate, 73rd International Symposium on Molecular Spectroscopy, Talk TH02, June 19, 2018. observed experimentally. These studies have been limited to the microwave regime between 7 to 26 GHz. The observed spectra of both molecules are dense due to the splittings that occur because of the low barriers to internal motion. Here we present our findings, analysis of the unidentified lines that are present in our experimental results, and our progress to extend the spectra of methanol dimers and methanol-argon clusters from 50 to 1000 GHz.

TC02 8:48 – 9:03 ANALYSIS OF THE ROTATIONAL SPECTRUM OF LARGE DIFLUOROMETHANE CLUSTERS TC04 9:24 – 9:39 RELAXATION DYNAMICS OF NEUTRAL IRON OXIDE CLUSTERS USING FEMTOSECOND PUMP-PROBE SPEC- LUCA EVANGELISTI, Dep. Chemistry ’Giacomo Ciamician’, University of Bologna, Bologna, Italy;ANNA TROSCOPY FIORINI, LUCA ZERBINI, LUCA FOSCHINI, Department of Computer Science and Engineering, University a b of Bologna, Bologna, Italy; CAMILLA CALABRESE ,EMILIOJ.COCINERO, Departamento de Qu´ımica JACOB M GARCIA, School of Molecular Sciences and Biodesign Center for Applied Structural Discovery, Ari- F´ısica, Universidad del Pa´ıs Vasco (UPV-EHU), Bilbao, Spain; BERHANE TEMELSO, Division of Information zona State University, Tempe, AZ, USA; SCOTT G SAYRES, School of Molecular Sciences, Arizona State Uni- Technology, College of Charleston, Charleston, SC, USA; GEORGE C SHIELDS, Department of Chemistry, versity, Tempe, AZ, USA. Furman University, Greenville, SC, USA; BROOKS PATE, Department of Chemistry, The University of Virginia, Charlottesville, VA, USA. Iron oxides have been used in a number of societally important catalytic processes; however, the molecular-level details behind their reaction mechanisms have been a challenge to observe. Molecular clusters have gained experimental attention In the last few years the development of chirp pulsed Fourier transform microwave (CP-FTMW) spectrometers has due to their ability to model bulk materials, ease of production, and direct application for gaining atomic level insights. Using enables the studies of relatively large rotors and observations of molecular clusters that were difficult to detect previously. In laser ablation combined with femtosecond pump-probe spectroscopy, the gas-phase dissociation and excitation-relaxation this work we present the study of large oligomers of difluoromethane ((CH2F2)n, with n from 5 to 7) for which experimental dynamics of neutral iron clusters in the presence of oxygen are observed. Dissociation/fragmentation time of neutral iron measurements were obtained during a collaboration between different research groups (especially at the University of Virginia oxide clusters from (FeO) (n = 1-10) decreases with increased molecular size from >300 fs to ∼150 fs. Clusters deviating c d n –USA and Universidad del Pa´ıs Vasco – Spain ). State-of-the-art quantum chemical calculations and structural results for from the 1:1 stoichiometry are generally seen to increase in relaxation time, owing to an increased stability induced by a the molecular species will be presented. The challenging decomposition of the spectrum into the individual rotational spectra caging effect from atomic oxygen. A notable example of dissociation stability is observed with the addition of O atoms from e for each species presented in the jet expansion will be carried out. In particular the approach using AUTOFIT algorithm Fe2 → Fe2O2 which decreases in relaxation time from >650 fs to <250 fs. The molecular-level insights from these cluster running on Amazon Web Service (AWS) and High Performance Computing (HPC) systems and its modified version for large studies provides a more comprehensive understanding for the design of future catalysts, leading to iron oxide materials with molecular system will be presented. increased reactivity and decreased impact. aInstituto Biofisika (CSIC UPV/EHU), 48080 Bilbao, Spain. bInstituto Biofisika (CSIC UPV/EHU), 48080 Bilbao, Spain. cBroadband Fourier transform rotational spectroscopy for structure determination: The water heptamer. C. Perez et al. Chem. Phys. Lett. 571 (2013) 1-15. dStructural Studies of Nicotinoids: Cotinine versus Nicotine. I. Uriarte et al. Chem. Eur. J. 23 (2017) 7238 -7244. eAUTOFIT, an automated fitting tool for broadband rotational spectra, and applications to 1-hexanal. N.A. Seifert et al. J. Mol. Spectrosc. 312 (2015) 13-21.

Intermission 86 87

TC05 10:18 – 10:33 TC08 11:12 – 11:27 − − PROGRESSIVE POLARIZATION OF PHENANTHRIDINE WITH INCREASING HYDRATION DEGREE EVIDENCED MODELING THE PHOTOELECTRON SPECTRA OF CeO2Bx (x=2, 3) AND CeB6 CLUSTERS BY QUADRUPOLE AND ITS COMPARISON WITH FORMAMIDE CLUSTERS HASSAN HARB, HRANT P HRATCHIAN, Chemistry and Chemical Biology, University of California Merced, PABLO PINACHO, AMANDA STEBER, DONATELLA LORU, MELANIE SCHNELL, FS-SMP, Deutsches Merced, CA, USA. Elektronen-Synchrotron (DESY), Hamburg, Germany. − Density functional theory calculations were used to explore the structures of Cerium oxide and boride clusters CeO2B2 , − − The structure of the microsolvated complexes of phenanthridine (PAN) with up to three water molecules has been inves- CeO2B3 -, and CeB6 . The results show intriguing structure and bonding trends, which are dependent on the ratio of boron tigated previously using chirped pulse Fourier transform microwave (CP-FTMW) spectroscopy from 2-8 GHz. In this work, centers to oxygens and the oxidation state of the cerium center. Natural ionization orbital analysis was also used to determine the effect of Resonance Assisted Hydrogen Bonding (RAHB), also called π–cooperativity, on those complexes has been stud- the nature electron detachment in photoelectron spectra of these species and to probe resulting electron rearrangement upon ied. In the resonant forms, the increase of the electronic density around the nitrogen nucleus enhances its hydrogen acceptor ionization. Such analysis allows us to differentiate between one-electron detachments and shake-up/shake-off transitions. capabilities. Thus, the main effects expected due to the resonance of the multiple conjugated π–bonds in the structure of the complexes are a strengthening of the hydrogen bonds and a lengthening of the N-C bonds. However, due to the subtle changes that occur on the molecular structure, the effect on the N-C distances could not be detected experimentally and only a shortening of the hydrogen bonds has been observed. Therefore, the use of the quadrupole coupling interactions as a probe for the polarization has been used to investigate these effects on the almost planar structures of PAN-(H2O)n n=1-3. This form of analysis has been shown to be effective in similar studies with formamide.a,b The experimental quadrupole coupling constant χcc shows a clear trend from isolated PAN to complexes with higher hydration degree, illustrating how the electronic environment at the 14N nucleus is altered by microsolvation.

aS. Blanco, P. Pinacho, J. C. Lopez,´ Angew. Chem. Int. Ed., 2016, 128, 9477-9481. bS. Blanco, P. Pinacho, J. C. Lopez,´ J. Phys. Chem. Lett., 2017, 8, 6060-6066.

TC06 10:36 – 10:51 HIGH-RESOLUTION INFRARED SPECTROSCOPY OF CARBON-SELENIUM CHAINS: SeC3Se and C3Se

THOMAS SALOMON, I. Physikalisches Institut, Universitat¨ zu Koln,¨ Koln,¨ Germany; YURY CHERNYAK, JOHN B DUDEK, Department of Chemistry, Hartwick College, Oneonta, NY, USA;JURGEN¨ GAUSS, Insti- tut fur¨ Physikalische Chemie, Universitat¨ Mainz, Mainz, Germany; STEPHAN SCHLEMMER, SVEN THOR- WIRTH, I. Physikalisches Institut, Universitat¨ zu Koln,¨ Koln,¨ Germany.

To date, carbon-selenium clusters have received little attention from both experiment and quantum-chemistry. Recent high-resolution infrared survey scans of the ablation products from carbon-selenium targets in the 5μm regime have revealed two bands previously not observed in the gas phase. On the basis of comparison with high-level quantum-chemical calcula- tions performed at the CCSD(T) level of theory these bands are attributed to the linear SeC3Se and C3Se chains. Following the microwave detection of diatomic CSe some 45 years agoa the present work marks the first high-resolution detection of polycarbon selenium clusters.

aJ. McGurk, H. L. Tigelaar, S. L. Rock, C. L. Norris, and W. H. Flygare, J. Chem. Phys. 58, 1420 (1973).

TC07 10:54 – 11:09 − A SPECTROSCOPIC EXPLORATION OF MoMnOy CLUSTERS AS HYDROGEN EVOLUTION CATALYSTS

ABBEY McMAHON, CARLEY N FOLLUO, JARRETT MASON, CAROLINE CHICK JARROLD, Depart- ment of Chemistry, Indiana University, Bloomington, IN, USA.

Due to its large band gap and uniquely layered crystalline structure, MoO3 is an attractive material in the field of organic photovoltaics. MoO3 has also been reported to exhibit photo- and electrochromic activity, and shows great promise as a catalyst, sensing material, and electrode in lithium-ion batteries. Previous studies have explored the reactivity of the MoxOy + H2O → MoxOy+1 + H2 reaction. This most recent study introduced Mn to the MoxOy structure in order to create a less oxophilic metal center. Photoelectron spectroscopy aided by a newly implemented planar ion funnel were utilized to probe − the unique electronic properties of anionic MoMnOy clusters reacted with H2O, to illuminate how this substituted element − impacted the two-centered mechanism of hydrogen evolution. Of particular interest were the structures of MoMnO4 when − produced by direct laser ablation and as a product of oxidation of MnMoO3 with H2O. 88 89 TD. Radicals Tuesday, June 18, 2019 – 8:30 AM TD03 9:06 – 9:21 INFRARED SPECTRUM OF (Z)-3-IODO-BUT-2-EN-1-YL [•CH2CHC(CH3)I] PRODUCED UPON PHOTODISSOCIA- Room: 217 Noyes Laboratory TION OF (Z)-1,3-DIIODO-BUT-2-ENE [(CH2I)HC = C(CH3)I]INSOLIDPARA-HYDROGEN

Chair: Sang Lee, Pusan National University, Busan, Korea KAROLINA ANNA HAUPA, Applied Chemistry, National Chiao Tung University, Hsinchu, Taiwan; YUAN-PERN LEE, Applied Chemistry, National Chiao Tung University, Hsinchu, Taiwan, Institute of Atomic and Molecular Sciences, Academia Sinica, Taipei, Taiwan.

Isoprene is the most abundant volatile organic compound (VOC) in the Earth’s atmosphere after methane. Ozonolysis of isoprene, with the production of the Criegee intermediate methyl vinyl ketone oxide (MVKO), plays an important role in a atmospheric chemistry. Recently, Barber et al. photolyzed 1,3-diiodo-but-2-ene [(CH2I)HC = C(CH3)I] in the presence TD01 8:30 – 8:45 of O2 with UV light and identified the Criegee intermediate syn-trans-MVKO as the main reaction product. However, the A SINGLE LONGITUDIANL MODE OPTICAL PARAMETRIC OSCILLATOR FOR HIGH RESOLUTION SPEC- detailed mechanism for the production of MVKO is unexplored. It was assumed that photolysis of (CH2I)HC = C(CH3)I at 2 TROSCOPY OF FREE RADICALS 248 nm results in preferential dissociation of the weaker allylic C(1)–I bond, rather than the vinylic (sp -hybridized) C(3)–I bond. Addition of O2 to the C(3) atom, followed by breaking the C(3)–I bond, produces the Criegee intermediate MVKO. QIANG ZHANGa, Photonics, Paul Scherrer Institute, Villigen, Switzerland; DEPING ZHANG, BOXING In this work we took the advantege of the diminished cage effect of solid para-hydrogen (p-H2) as a matrix host to study the ZHU, Department of Chemistry, University of Science and Technology of China, Hefei, China; YANG CHEN, UV photodissociation of (Z)-(CH2I)HC = C(CH3)I. We report the formation and infrared identification of (Z)-3-iodo-but- DONGFENG ZHAO, Hefei National Laboratory for Physical Science at Microscale, University of Science and 2-en-1-yl [•CH2CHC(CH3)I] radical intermediate upon photodissociation of (Z)-(CH2I)HC = C(CH3)I in solid p-H2 at Technology of China, Hefei, China. 3.3 K with light at 280 nm. Lines at 3115.6, 2025.2, 3001.2, 2933.2, 2880.3, 2835.8, 1474.9, 1409.6, 1406.7, 1375.5, 1265.3, −1 1061.8, 1018.5, 1008.6, 922.0, 913.7, and 792.5 cm are assigned to (Z)- • CH2CHC(CH3)I. The assignments were derived We present the development of a tunable, narrow-bandwidth optical parametric oscillator (OPO) system and its applica- according to behavior on secondary photolysis and comparison of the vibrational wavenumbers and the IR intensities of the tions in high resolution spectroscopy of free radicals. The OPO system employs a bulk KTP crystal as the nonlinear optical observed lines with values predicted with the B2PLYP-D3/cc-pVTZ-pp method. No evidence of breakage of the C(3)–I bond material and a compact grazing-incidence-grating cavity as the oscillator. The second harmonic output of an injection-seeded to form •C(CH3) = C(CH2I)H was observed. nanosecond Nd:YAG laser with a spatially optimized beam profile is used to pump the OPO system. The OPO cavity length is precisely controlled by monitoring both the beam position and the mode structure of the signal output, ensuring a stable aV. P. Barber et al. J. Am. Chem. Soc., 140, 10866-10880 (2018). single-longitudinal-mode operation of the system with a broad tuning range. The output of the OPO covers a tunable wave- length of 660 to 2700 nm, with a typical pulse duration of 5 ns, a FT-limited bandwidth 150 MHz, and a total pulsed energy of 2.5 mJ at a pump energy of 40 mJ. The newly developed OPO system has been applied to the laser induced fluorescence study on high resolution electronic spectra of free radicals in a supersonic jet expansion. As an example, fully resolved electonic spectra of C3 and YO radicals are presented.

aUniversity of Science and Technology of China

TD04 9:24 – 9:39 THE HIGH-RESOLUTION ELECTRONIC SPECTRUM OF THE SiCCl FREE RADICAL: PROBING THE CARBON- SILICON TRIPLE BOND TD02 8:48 – 9:03 THE ELECTRONIC SPECTRUM AND MOLECULAR GEOMETRY OF THE JET-COOLED STIBINO (SbH2)FREE DENNIS CLOUTHIER, GRETCHEN K ROTHSCHOPF, TONY SMITH, Laser Research Laboratory, Ideal RADICAL Vacuum Products, LLC, Albuquerque, NM, USA.

FUMIE X SUNAHORI, Department of Chemistry, Rose-Hulman Institute of Technology, Terre Haute, IN, USA; The 600-515 nm electronic band system of the jet-cooled SiCCl free radical has been studied by laser-induced fluores- DENNIS CLOUTHIER, TONY SMITH, Laser Research Laboratory, Ideal Vacuum Products, LLC, Albu- cence and single vibronic level emission spectroscopy. The radical was produced in an electric discharge through a dilute querque, NM, USA. mixture of 1,1-dichlorosilacyclobutane in high pressure argon. The low-resolution LIF spectrum exhibits bands involving all three excited state vibrations, establishing values for the upper state vibrational frequencies. Emission spectra from thirteen The jet-cooled stibino (SbH2) free radical has been detected for the first time. This highly reactive species was produced upper state levels yielded the ground state bending and stretching energy levels up to 5000 cm−1. These were satisfactorily in an electric discharge through a precursor mixture of stibine (SbH3) diluted in high pressure argon. Stibine was synthesized fitted to a Renner-Teller model that included spin-orbit and vibrational anharmonicity effects. A high-resolution rotationally by the low-temperature reduction of SbCl3 with LiAlH4 and stored and handled at -85 oC to avoid decomposition. Low- 2Π resolved spectrum of the 3/2 spin-orbit component of the 0-0 band was recorded and rotational analysis yielded accurate resolution LIF scans revealed a single band of SbH2 with complex rotational structure in the 514.9 - 511.0 nm region. We B values for both states of SiC35Cl and SiC37Cl. These constants were used with fixed ab initio C-Cl bond lengths to obtain find that the fluorescence lifetimes of the rotational transitions in this band are very short, of the order of 50-75 ns, suggesting r = 1.692(1) Aand˚ r =1.594(1)A.˚ The bond lengths correspond to a silicon-carbon double bond in the ground state and ˜ 2 ˜ 2 an upper state dissociative process. The spectrum is assigned to the A A1 - X B1 electronic transition by analogy with the an unusual Si-C triple bond in the excited state, similar to our previous findings for SiCH and SiCF. Halogenation has little known spectra of NH2,PH2 and AsH2 and in accord with a recent high level ab initio study. Emission spectra obtained effect on the Si-C bond length in both states. after laser excitation of single rotational lines in the 0-0 band show a ground state bending frequency of approx. 820 cm−1, consistent with theoretical predictions. The rotationally resolved spectrum of the 0-0 band, which spans some 150 cm−1, was recorded at a resolution of 0.08 cm−1and analyzed in detail. The spectrum is complicated by large spin splittings and Sb hyperfine effects. The molecular constants were used to determine the geometry of SbH2 in both states.

Intermission 90 91

TD05 10:18 – 10:33 TD07 10:54 – 11:09 ˜ 2 HIGH RESOLUTION IR SPECTROSCOPY OF MONOHALOCARBENES: THE CH STRETCH FUNDAMENTAL AND VIBRONIC STRUCTURE OF THE NO3 X A2 SYSTEM VIBRATIONAL COUPLING IN HCF MASARU FUKUSHIMA, Information Sciences, Hiroshima City University, Hiroshima, Japan. KIRSTIN D DONEY, JILA and NIST, University of Colorado, Boulder, CO, USA; ANDREW KORTYNA, PRE- ˜ 2 STON G. SCRAPE, JILA, National Institute of Standards and Technology and Univ. of Colorado, Boulder, CO, The X A2 state of NO3 under jet cooled conditions is investigated via laser induced fluorescence ( LIF ) and two-color USA; DAVID NESBITT, Department of Chemistry, JILA CU-NIST, Boulder, CO, USA. resonant four-wave mixing ( 2C-R4WM ) techniques. The electronic structure of NO3 is thought to be similar to that of BF3, ab and the latter has been well documented in the literatures .TheBF3 highest occupied molecular orbital ( HOMO ) possesses We present first results from high-resolution infrared study of jet-cooled singlet monofluorocarbene (HCF) in the CH peculiar electronic structure with orbital localization on each of three F’s and no contribution on the center atom, B. For −1 ˜ 2 ˜ 2 ˜ 2 stretch region near 2600 cm . Fully rotationally resolved absorption spectra of the CH stretch (ν1) fundamental band, the NO3, the HOMO corresponds to a singly occupied molecular orbital ( SOMO ), and, in the X A2 state ( A E and B E , ← ν1+ν3 ν3 hot band, and part of the ν2+ν3 combination band are observed and analyzed, representing first experimental too ) of NO3, the un-paired electron is localized on the three O’s and has no contribution on N. For this state, the degenerate determination of rovibrational constants for these upper/lower levels. Transitions accessing each of the ν1 Ka =0,1and vibrations are naturally expected to strongly affect the electron motion, which can be referred to as ”degenerate-vibrationally 2 manifolds are observed, with clear evidence for strong rovibrational coupling between the ν1 Ka =2andν2+ν3 Ka =3 induced vibronic coupling” on the non-degenerate electronic state. The SOMO characteristics of NO3 have been confirmed manifolds and allowing for perturbation analysis of a c-type Coriolis interaction between these two levels. The inclusion by high-level quantum chemical computationc. The characteristic features of the vibrational structure of the X˜ 2A state 2 of such Coriolis coupling explains the large perturbations in both line positions and intensities observed for Ka =2and3 may possibly be understood by the vibronic coupling. One feature is an unexpectedly large spin splitting of 10 (=NK )of d subbands of the ν1 and ν2+ν3 rovibrational bands, respectively. The results are in good agreement with, and also significantly the 3ν4 (a1) level observed by 2C-R4WM , and this splitting can be understood as the good quantum number behavior of P extend, the analyses from previous studies of HCF using stimulated emission pumping from the first electronically excited ( = Kv +Σ=Λ+l +Σ) derived from the coupling. state. aH. B. Gray, Electrons and Chemical Bonding, W. A. Benjamin Inc., New York (1965); Open Source Tex Books, https://archive.org/details/ost-chemistry- electrons chemical bonding (retrieved Feb. 26, 2019). bF. A. Cotton, Chemical Applications of Group Theory, 2nd ed., Wiley-International, New York (1971). cW. Eisfeld and K. Morokuma, J. Chem. P hys. 113, 5587 (2000). dM. Fukushima and T. Ishiwata, 73rd ISMS, paper WD02 (2018).

TD08 11:12 – 11:27 − VIBRATIONAL SPECTROSCOPY OF CS2 RADICAL ANION IN WATER

TD06 10:36 – 10:51 IRENEUSZ JANIK,G.N.R.TRIPATHI,Radiation Laboratory, University of Notre Dame, Notre Dame, IN, USA. EXPERIMENTAL EVIDENCE OF THE ν3 MODE IN NO3 VIA SLOW PHOTOELECTRON VELOCITY-MAP IMAGING − OF COLD NO − 3 Recent transient Raman studies of the CO2 radical in water have led to the vibrational properties of this important radical intermediate. More importantly the evidence of the electron being shared between the bent CO2 and its hydration MARK C BABIN, Department of Chemistry, University of California - Berkeley, Berkeley, CA, USA; JESSALYN shell at an energy of about ˜ 0.28 eV above the ground electronic state is obtained. The corresponding electronic state A. DeVINE, Department of Chemistry, University of California at Berkeley, Berkeley, CA, USA;JOHNF.STAN- has a life-time of several femtoseconds, consistent with the theoretical value. No evidence of non-equivalence of the two TON, Quantum Theory Project, University of Florida, Gainesville, FL, USA; DANIEL NEUMARK, Department CO bonds was found, which suggested that the partially detached electron is symmetrically situated between CO2 and the of Chemistry, The University of California, Berkeley, CA, USA. water molecule. Because of the electron not being localized on CO2, the Raman scattered photon does not terminate into a − 1 vibrational state corresponding to the CO2 overtones above 0.28+/-0.03 eV or higher. Now in a follow up study, we have With five electronic states within 2 eV, the nitrate radical (NO3) has a rich vibronic landscape for which photoelectron − examined its sulfur analogue CS2 . We have prepared the radical anion in water by pulse radiolysis with Raman detection up spectroscopy is an ideal probe. Here, we use slow photoelectron velocity map imaging of cryogenically cooled anions (cryo- −1 ˜ 2 to 4000 cm to monitor its vibrational fingerprints. The Raman spectrum, excited in the resonance with the 270 nm (λmax) SEVI), a high-resolution variant of anion photoelectron spectroscopy, to investigate the vibronic structure of the X A2 state − −1 2 cm of NO3. Our cryo-SEVI spectra are in excellent agreement with Franck-Condon simulations produced using a three-state absorption of CS is dominated by a very strong band at 666 , associated with the symmetric C-S stretching vibration, its overtones, and combinations with SCS bending vibration of 330 cm−1. Solvation shell bending and stretching modes are Koppel-Domke-Cederbaum¨ (KDC) Hamiltonian constructed for the NO3 radical. Together, the experimental and simulated − −1 2 spectra provide clear evidence that the ν3 fundamental resides near 1060 cm , resolving a long-standing controversy sur- also enhanced, suggesting contribution to the excited state of the radical anion analogous to CO . From the progression of overtones, and the first order anharmonicity of 2.57cm−1, we estimate a continuum of vibrational states at an energy of rounding this vibrational fundamental. Further, the appearance of activity along the ν4 mode in this cryogenically-cold system − − roughly 5.4 eV. Unlike CO2 ,CS2 did not show any evidence of electron detachment up to the energies of 0.5eV. DFT verifies its activity through a Herzberg-Teller interaction, rather than as a hot band as previously suggested. − calculations reproduced experimental frequencies fairly well predicting a molecular geometry of CS2 with CS bond lengths of 1.638Aand˚ CSC angle of 143.3o. − (1) Janik I.,Tripathi G.N.R.; The nature of the CO2 radical anion in water. J. Chem. Phys. 2016, 144, 154307. 92 93 TE. Fundamental interest TD09 Post-Deadline Abstract 11:30 – 11:45 Tuesday, June 18, 2019 – 8:30 AM SPECTROSCOPY AND DYNAMICS OF QUANTUM STATE CONTROLLED SIO+ Room: B102 Chemical and Life Sciences Chair: Jens-Uwe Grabow, Gottfried-Wilhelm-Leibniz-Universitat,¨ Hannover, NI, Germany IVAN ANTONOV, PATRICK R STOLLENWERK, SRUTHI VENKATARAMANABABU, BRIAN C. ODOM, Department of Physics and Astronomy, Northwestern University, Evanston, IL, USA.

New tools for cooling and internal state control of molecules emerged in the past decade that allowed fast progress in the field of ultracold molecules. In this work, control of the rotational state of trapped ultracold SiO+ was utilized to study TE01 8:30 – 8:45 + its spectroscopy and reaction dynamics. SiO was prepared by laser ablation of SiO followed by 1+1 REMPI. The ions 2(0−) + EXTENSIVE HIGH-RESOLUTION PHOTOASSOCIATION SPECTRA AND PERTURBATION ANALYSIS OF were trapped in an RF Paul trap and sympathetically cooled by co-trapped ultracold atomic Ba ions. Rotational states of LONG-RANGE STATE OF ULTRACOLD RbCs MOLECULES SiO+ were cooled and controlled by means of optical pumping with a spectrally pulse-shaped broadband light source. The 2 2 + pumping via the B Σ-X Σ electronic transition on rotational lines with selected N and ΔN was used to cool SiO molecules DIANQIANG SU, ZHONGHUA JI, YANTING ZHAO, State Key Laboratory of Quantum Optics and Quantum to the ground rotational state and to create a narrow distribution of occupied rotational states centered on a targeted level. Optics Devices, Institute of Laser Spectroscopy, Shanxi University, Taiyuan, Shanxi, China; CHUANLIANG + Populations centered at different rotational states ranging from N=3 to N=65 were created. SiO quantum states were probed LI, Department of Physics, School of Applied Science, Taiyuan University of Science and Technology, Taiyuan, 2 2 2 with photodissociation spectroscopy via the C Π-X Σ electronic transition. The C Π state was experimentally characterized Shanxi, China; JINJUN LIU, Department of Chemistry, University of Louisville, Louisville, KY, USA. for the first time. Rotational state control was used to facilitate line assignment and to probe high rotational levels of the 2 + − X Σ state unpopulated at room temperature. Reaction of trapped SiO with H2 was studied. The reaction rate of rotationally We report high-resolution photoassociation (PA) spectra of RbCs in the 2(0 ) long-range state. Transitions to more than + −1 “thermal” SiO was found to be in good agreement with the literature value. The reaction rates of thermal H2 with ultracold fifty vibrational levels were recorded with the largest binding energy being 507.5 cm . By fitting the experimental transition + + − rotational state controlled SiO were measured. Reaction of H2 with SiO “super rotor” states in which rotational energy is frequencies to the improved LeRoy-Bernstein formula, the C6 coefficient for the potential energy curve of the 2(0 ) state − of the same order as bond dissociation energy and rotational period approaches time of collision was studied. was determined to be -1509±97 a.u.. Perturbation-induced energy level shift and state mixing of the long-range 2(0 ) and 3(1) states have been analyzed using an effective Hamiltonian that may be applied to mixing between other excited states of RbCs, as well as other heteronuclear diatomic molecules. Experimentally observed PA transitions to the v = 190 vibrational Post-Deadline Abstract TD10 11:48 – 12:03 level of the 2(0−) state and a vibrational perturbing level in the 3(1) state have been fit using the effective Hamiltonian, which CAVITY RING-DOWN SPECTROSCOPY OF JET-COOLED YO MOLECULES provides the accurate value of the perturbation coefficient β0. The experimentally determined rovibronic structure and the deperturbation analysis provide critical information for the search of new schemes for efficient production of ultracold RbCs ANAM C. PAUL, HAMZEH TELFAH, Department of Chemistry, University of Louisville, Louisville, KY, USA; molecules in the ground state. XIYE HU, Department of Physics, University of Illinois at Urbana-Champaign, Urbana-Champaign, IL, USA; JINJUN LIU, Department of Chemistry, University of Louisville, Louisville, KY, USA.

Yttrium (II) oxide (YO) is one of the first molecules that have been laser-cooled. Although the laser-cooling cycle in a ˜2 ˜ 2 + ˜ 2 TE02 8:48 – 9:03 the reported experiment involves the Π1 2 − Σ (0, 0) transition, “dark” electronic states such as ’ Δ3 2 also play A / X A / + ˜ 2Δ − ˜ 2Σ+ HIGH-RESOLUTION ROTATIONAL SPECTROSCOPY AND COHERENT CONTROL OF CaH important roles and directly affect the cooling efficiency. Moreover, the forbidden A’ 3/2 X transition can be utilized for further cooling of YO molecules.b To better understand the ro-vibronic structure of YO, we have obtained and analyzed ˜2 ˜ 2 + CHIN-WEN CHOU, Time and Frequency Division, National Institute of Standards and Technology, Boulder, the cavity ring-down (CRD) spectrum of the A Π3 2 1 2 − X Σ (0, 0) transition of jet-cooled YO molecules. Detection of / , / CO, USA; YIHENG LIN, CAS Key Laboratory of Microscale Magnetic Resonance and Department of Modern ˜ 2Δ − ˜ 2Σ+ the A’ X (0, 0) transition is in process. We will discuss experimental measures that will be taken to further improve Physics, University of Science and Technology of China, Hefei, China; ALEJANDRA COLLOPY, CHRISTOPH the signal-to-noise ratio for the pursuit of “dark”-state spectra of YO and other candidate molecules for laser cooling. KURZ, TARA FORTIER, SCOTT DIDDAMS, DIETRICH LEIBFRIED, Time and Frequency Division, National aM. T. Hummon, M. Yeo, B. K. Stuhl, A. L. Collopy, Y. Xia, and J. Ye, Phys. Rev. Lett. 110, 143001 (2013) Institute of Standards and Technology, Boulder, CO, USA; DAVID LEIBRANDT, Time and Frequency Division, bA. L Collopy, M. T Hummon, M. Yeo, B. Yan, and Jun Ye, New J. Phys. 17, 055008 (2015) National Institute of Standards and Technology, Department of Physics, University of Colorado, Boulder, CO, USA.

We demonstrate methods for precision spectroscopy and coherent quantum state manipulation of a molecular ion, based on quantum-logic spectroscopy [1-3]. In thermal equilibrium with room temperature blackbody radiation, the electronic and vibrational degrees of freedom of the proof-of-principle CaH+ molecule are in their ground states. We laser cool the coupled translational motion of a co-trapped Ca+ atom and the molecule to near its ground state [4]. Subsequently, we coherently drive rotational Raman transitions using two beams derived from a single frequency laser that is far off-resonance from any molecular transition. Information regarding the molecular states is transferred to the atomic ion using the coupled harmonic motion as an information bus [1-3] and read out via state-dependent fluorescence detection without disturbing the molecular state. In this way, we initialize the molecular ion in a pure quantum state in a probabilistic but heralded fashion [3]. Following preparation, we can drive further rotational transitions up to the THz range with two beams derived from a single, far-off- resonant frequency comb [5, 6]. The final states of the transitions are detected, enabling unambiguous assignment of the observed signals to the corresponding transitions. For CaH+, we have measured the frequency of THz rotational transitions with sub-kHz resolution, and improvement to the sub-Hz level seems feasible [7]. This protocol can be extended to investigate coherent rotational-vibrational transitions of a large class of diatomic and polyatomic molecules in the optical and infrared domains. [1] P. O. Schmidt et al., Science 309, 749 (2005). [2] F. Wolf et al., Nature 530, 457 (2016). [3] C. W. Chou et al., Nature 545, 203 (2017). [4] M. D. Barrett et al., Phys. Rev. A 68, 042302 (2003). [5] D. Leibfried, New J. Phys. 14, 023029 (2012). [6] S. Ding and D. N. Matsukevich, New J. Phys. 14, 023028 (2012). [7] A. Bartels et al., Opt. Lett. 29, 1081 (2004). 94 95

TE03 9:06 – 9:21 TE06 10:00 – 10:15 LAMB DIP MEASUREMENTS OF MOLECULES WITH KHZ ACCURACY IN THE MID-INFRARED ANOMALOUS ZEEMAN SPLITTING IN THE ROVIBRATIONAL SPECTRUM OF THE OH RADICAL SOLVATED IN SUPERFLUID HELIUM or: HOW I LEARNED TO STOP WORRYING AND LOVE THE PROVERBIAL DROPLET CUNFENG CHENG, ZITAN ZHANG, YU ROBERT SUN, AN-WEN LIU, SHUI-MING HU, Hefei National EFFECTS Laboratory for Physical Science at Microscale, University of Science and Technology of China, Hefei, China. GARY E. DOUBERLY, Department of Chemistry, University of Georgia, Athens, GA, USA. Precision spectroscopy of molecules in the mid-infrared region where the fundamental bands are located is of great interest in fundamental physics. In order to achieve a high accuracy, one can measure the spectroscopy in the Lamb-dip zone The hydroxyl radical was doped into a helium droplet, and a laser/droplet interaction zone was subjected to a homoge- with sub-Doppler resolution, where further reduction of the laser linewidth and transit-time broadening is perspective. Here neous 0.425(2) Tesla magnetic field. Mid-infrared Zeeman spectroscopy reveals splittings of the Q(3/2) Λ-doublet transitions we report a new method to reduce the mid-infrared laser linewidth of an optical parametric oscillator (OPO) by locking the that are 21 % larger than those predicted by both degenerate perturbation theory and a variational treatment of the Zeeman pump and idle lights to a frequency comb, resulting in a narrow linewidth and good long-term stability of the signal laser. In effect. This implies simply that the product geBΩeff is 21 % larger in superfluid helium than in the gas-phase. Although this way, we demonstrate that the measured Lamb dip linewidth can be as narrow as tens of kHz and the transition frequency speculative, it is interesting to consider the results in the context of the Einstein-de Haas effect, in which coupling to droplet can be determined to an accuracy of a few kHz. phonons induces a renormalization of the electron g factor.a

aJ.H. Mentink, M.I. Katsnelson, M. Lemeshko, Quantum many-body dynamics of the Einstein-de Hass effect, Phys. Rev. B, 99, 064428 (2019).

TE04 9:24 – 9:39 CP-FTMMW SPECTROSCOPY OF HIGH- RYDBERG STATES OF NO

TIMOTHY J BARNUM, JUN JIANG, ROBERT W FIELD, Department of Chemistry, MIT, Cambridge, MA, USA.

Since the pioneering work of Miescher in the 1960s, the Rydberg states of nitric oxide have held the attention of spec- troscopists due to the prototypical energy level structure and rich non-radiative dynamics, which have, in turn, confirmed and challenged existing theory. This work describes a new approach to investigate the relatively underexplored regime of Intermission high orbital angular momentum () Rydberg states via chirped-pulse Fourier transform millimeter-wave (CP-FTmmW) spec- troscopy. We have prepared high-n (n ≥ 27), high- ( ≥ 4) Rydberg states of NO by a triple resonance laser excitation through the low-lying 4f state, followed by mmW excitation. The mmW field polarizes Rydberg-Rydberg transitions within the bandwidth of our spectrometer (220-330 GHz) and the free induction decay is phase-coherently detected and digitized on a fast oscilloscope. The observed transitions are interpreted in the framework of a long-range electrostatic model for the TE07 10:54 – 11:09 Rydberg energy level structure, resulting in improved determination of the electric structure (multipole moments, polarizabil- FINE AND HYPERFINE STRUCTURE OF 173YbF ity) of the NO+ ion-core. In addition, we will discuss the role of electric fields, hyperfine structure, and non-radiative decay mechanisms – predissociation and autoionization – on the observed mmW spectra. HAILING WANG, Physics Department , East China Normal University , Shanghai, China;TIMO- THY STEIMLE, School of Molecular Sciences, Arizona State University, Tempe, AZ, USA; RICHARD MAWHORTER, Department of Physics and Astronomy, Pomona College, Claremont, CA, USA;JENS-UWE GRABOW, Institut fur¨ Physikalische Chemie und Elektrochemie, Gottfried-Wilhelm-Leibniz-Universitat,¨ Han- TE05 9:42 – 9:57 nover, Germany. + AN INFRARED PHOTODISSOCIATION SPECTROSCOPIC AND THEORETICAL STUDY OF M(CO)6,7,8 (M = Ti, Zr, 174 Hf) YbF has been used for some time in attempts to determine the electrostatic T,P violating electron electric dipole moment (eEDM). It was recently pointed out [1] that 173YbF may be an avenue for determining an EDM induced by the 173 SHUJUN LEI, JIAYE JIN, MINGFEI ZHOU, Fudan University, Department of Chemistry, Shanghai, China. magnetic quadrupole moment (MQM). As in the eEDM case, here the molecular properties of YbF are experimentally advantageous. We report a detailed analysis of the fine and hyperfine structure in the X2σ+ state from a combined analysis Spectroscopic and theoretical study of extreme coordinated metal carbonyl complexes has been a subject of intensive of rotational and optical transitions. Numerous hyperfine components in the N=4 ¿ 5 and N=3 ¿ 4 rotational transitions were a + studies. M(CO)n (M = Ti, Zr, Hf) ions were produced by ablating a metal target in a pulse of CO seeded helium, and further recorded using a separated field pump/probe microwave optical double residence technique. Fourier transform microwave + studied by mass-selected infrared photodissociation spectroscopy in the carbonyl stretching region. Ti(CO)6 is formed as spectroscopy was used to record five features of the N=0 ¿ 1 rotational transition. This rotational data was combined with + 2 2 + dominant species in the mass spectrum, while M(CO)6,7,8 ions are of the most abundant species in the mass spectra for precisely measured (0,0) A π1/2 -X σ optical transitions of a cold molecular beam sample. Resulting fine and hyperfine + b zirconium and hafnium. The infrared spectra of M(CO)6 (M = Ti, Zr, Hf) show good agreement with previous reports. parameters will be discussed and compared with recent theory [2]. + M(CO)7 (M = Zr, Hf) ions only dissociate under focused laser irradiation and have one broad band, indicating strongly The research at Arizona State University was supported by a grant from the Heising Simons Foundation (Grant 2018- + coordinated complexes. M(CO)8 (M = Zr, Hf) complexes can fragment by one CO molecule in unfocused light, and each 0681). −1 −1 + exhibits an infrared band centered at 2084 cm (Zr) and 2072 cm (Hf). Theoretical calculations indicate that the M(CO)7 1. V.V. Flambaum, et al., arXiv:1810.02477v2 [hep-ph] (10 Dec 2018) + (M = Zr, Hf) complexes are at doublet ground states with C2v symmetry. The M(CO)8 (M = Zr, Hf) complexes are identified 2. P. Schwerdtfeger, et al., Mol. Phys. 114, 1110 (2016) as 19-electron octacarbonyls. Each of them has D4 symmetry (distorted cubic geometry) and a doublet ground state. The results extend the knowledge of extreme coordinated carbonyl complexes to Group 4 metals, and provide insights into the ion growth mechanisms in the gas phase.

aZhou, M. F.; Frenking, G. Angew. Chem. Int. Ed. 2018, 57(21), 6236-6241; Science, 2018, 361(6405), 912-916. bDuncan, M. A. J. Phys. Chem. A, 2013, 117(46), 11695–11703. 96 97

TE08 11:12 – 11:27 TE10 11:48 – 12:03 a + AN ELECTRONIC SPECTROSCOPIC STUDY OF A MOLECULAR BEAM SAMPLE OF YbOCH3 THEORETICAL STUDY OF ThO AND HfF FOR ELECTRON ELECTRIC DIPOLE MOMENT SEARCH EXPERI- MENTS TIMOTHY STEIMLE, ANH T. LE, EPHRIEM TADESSE MENGESHA, School of Molecular Sciences, Ari- zona State University, Tempe, AZ, USA; BENJAMIN AUGENBRAUN, ZACK LASNER, JOHN M. DOYLE, ALEXANDER PETROVa, LEONID SKRIPNIKOVb,ANATOLYTITOV,Division of Innovations, NRC “Kur- Department of Physics, Harvard University, Cambridge, MA, USA. chatov Institute” PNPI, Gatchina, Leningrad region, Russia.

Ytterbium monofluoride, YbF, has long been used as a venue in attempts to measure the electron electric dipole moment Theoretical study of ThO and HfF+ for the experiments to search for the electron electric dipole moment (eEDM) are (eEDM) b,c. As pointed out by Kozyryev and Hutzler d, Yb containing symmetric top molecules are expected to exhibit reported. The g-factors [1,2], effective electric field in the molecule acting on the eEDM [3], hyperfine structure, Zeeman and 3 enhanced sensitivity for EDM measurements, relative to YbF. This is largely due to the ease of polarization of the K = 1 Stark effects [3,4,5] (including dynamic) for the eEDM sensitive Δ1 states are calculated with high accuracy. Calculations rotational levels. Here we report on our initial molecular beam studies of the heretofore unknown molecules YbOCH3 and are required for interpretation of the experiments and estimation of systematic effects. YbOCD3. Broad survey scans using two dimensional (excitation vs dispersed fluorescence) spectroscopy in the 600-480 nm range were recorded. An intense band detected near 579 nm is assigned to the origin band of the electronic transition 1. A.N. Petrov, L.V. Skripnikov, A.V. Titov, N.R. Hutzler, P.W. Hess, B.R. O’Leary, B. Spaun, D. DeMille, G. Gabrielse, of YbOCH3. The high-resolution (∼ 30 MHz) laser induced fluorescence (LIF) spectrum of this band was recorded both and J.M. Doyle, Phys.Rev.A 89, 062505 (2014) field-free and in the presence of a static electric field. The dispersed fluorescence resulting from the excitation of rotation- ally resolved branch features has been analyzed to produce fluorescence branching ratios. Implications for planned EDM 2. A. N. Petrov, L. V. Skripnikov, and A. V. Titov, Phys. Rev. A 96, 022508 (2017) measurements will be presented. 3. A.N. Petrov, Phys.Rev.A, 91, 062509 (2015)

aFunded by a grant from the Heising-Simons Foundation. bHudson, J. J.; Sauer, B. E.; Tarbutt, M. R.; Hinds, E. A., Measurement of the Electron Electric Dipole Moment Using YbF Molecules. Phys. Rev. Lett. 2002,89(2), 4. A. N. Petrov, Phys. Rev. A 95, 062501 (2017) 023003/1-023003/4. cTarbutt, M. R.; Sauer, B. E.; Hudson, J. J.; Hinds, E. A., Design for a fountain of YbF molecules to measure the electron’s electric dipole moment. New J. Phys. 2013, 15 5. A.N. Petrov, Phys.Rev.A, 97, 052504 (2018) (May), 053034/1-053034/17. dKozyryev, I.; Hutzler, N. R., Precision measurement of time-reversal symmetry violation with laser-cooled polyatomic molecules. arXiv.org, e-Print Arch., Phys. 2017, 1-11. aAlso at Division of Quantum Mechanics, St. Petersburg State University, Russia bAlso at Division of Quantum Mechanics, St. Petersburg State University, Russia

TE09 11:30 – 11:45 THE BENDING MODES OF YbOH PROBED BY VISIBLE SPECTROSCOPY

TIMOTHY STEIMLE, School of Molecular Sciences, Arizona State University, Tempe, AZ, USA; HAILING WANG, Physics Department , East China Normal University , Shanghai, China; EPHRIEM TADESSE MENGE- SHA, School of Molecular Sciences, Arizona State University, Tempe, AZ, USA;NICKOLASPILGRAM, NICHOLAS R HUTZLER, Division of Physics, Mathematics and Astronomy, California Institute of Technol- ogy, Pasadena, CA, USA.

Ytterbium monofluoride, YbF, has long been used as a venue in attempts to measure the electron electric dipole mo- ment (eEDM)1−2 . In addition to the molecular EDM resulting from the eEDM contribution, the 173Yb (16.1%, I=5/2) isotopic form of Yb-containing molecules are also expected to have an EDM caused by an interaction of a nuclear magnetic quadrupole moment (NMQM)3 with the electrons. As pointed out by Kozyryev and Hutzler4,theX2Σ+(0110) level of YbOH is expected to exhibit enhanced sensitivity for EDM measurements, relative to YbF, largely due to the ease of polarization. The degenerate bending vibrational levels of YbOH are poorly characterized5. Here we report on high-resolution studies of 2Π 2Σ+ 2Π 2Σ+ the molecular beam of the A 1/2-X (010-000) and A 1/2-X (010-010) transitions of YbOH. In addition, the dispersed fluorescence resulting from the excitation of rotationally resolved branch features has been analyzed to produce fluorescence branching ratios. Implications for planned EDM measurements will be presented. Funded by a grant from the Heising-Simons Foundation. References: 1.Hudson, J. J.; Sauer, B. E.; Tarbutt, M. R.; Hinds, E. A., Phys. Rev. Lett. 2002, 89 (2), 023003/1-023003/4. 2.Tarbutt, M. R.; Sauer, B. E.; Hudson, J. J.; Hinds, E. A., New J. Phys. 2013, 15 (May), 053034/1-053034/17. 3.Lackenby, B. G. C.; Flambaum, V. V., Nucl. Theory 2017, 1-7. 4.Kozyryev, I.; Hutzler, N. R., arXiv.org, e-Print Arch., Phys. 2017, 1-11. 5.Melville, T. C.; Coxon, J. A., J. Chem. Phys. 2001, 115 (15), 6974-6978. 98 99 TF. Dynamics and kinetics Tuesday, June 18, 2019 – 8:30 AM TF03 9:06 – 9:21 Room: 2079 Natural History ULTRAFAST COHERENT DISSOCIATION DYNAMICS IN NITROTOLUENE RADICAL CATIONS Chair: Kyle N. Crabtree, University of California, Davis, CA, USA DERRICK AMPADU BOATENG, KATHARINE MOORE TIBBETTS, Chemistry, Virginia Commonwealth University, Richmond, VA, USA.

The ultrafast dynamics of polyatomic radical cations contribute to important processes including initiation of detonation in energetic molecules, radiation-induced DNA damage, and chemical reactions in the upper atmosphere and space. Probing TF01 8:30 – 8:45 these dynamics in the gas phase is challenging due to the rapid dissociation of many polyatomic radical cations following electron removal. This presentation will discuss how the pump-probe technique of femtosecond time-resolved mass spec- CHARACTERIZATION OF THE HIGHLY DYNAMIC INTERFACE IN THE PLASTOCYANIN-CYTOCHROME fCOM- trometry (FTRMS) can be a powerful tool for understanding time-resolved vibrational and dissociation dynamics of isolated PLEX BY SITE-SPECIFIC 2D IR radical cations and will highlight recent results in our laboratory on 2-, 3-, and 4-nitrotoluene (NT), which serve as model SASHARY RAMOS, AMANDA L LE SUEUR, Department of Chemistry, Indiana University, Bloomington, IN, systems for nitroaromatic explosives such as TNT. Our experiments use strong-field, near-infrared (1200–1600 nm) pulses USA; RACHEL E. HORNESS, Department of Chemistry, Rose-Hulman Institute of Technology, Terre Haute, IN, to induce adiabatic tunneling ionization, which prepares a large population of radical cations in the ground state that are USA; MEGAN THIELGES, Department of Chemistry, Indiana University, Bloomington, IN, USA. amenable to subsequent optical excitation. The resulting electronically cold radical cation is typically prepared in a coherent superposition of highly excited vibrational states, i.e., as a nuclear “wave packet”. Excitation of the wave packet by the probe Protein conformational heterogeneity and dynamics, in particular those of protein side-chains, are of importance to pulse at particular time delays accesses electronic excited states that lead to dissociation, thereby resulting in oscillations in protein function. Experimentally characterizing the contribution of these motions to function is complicated due to the diverse the ion yields of the parent and fragment ions as a function of pump-probe delay. These coherent dynamics drive C–NO2 timescales and spatial heterogeneity inherent to proteins. Two-dimensional infrared (2D IR) spectroscopy has emerged as a bond dissociation in all three NT isomers, with each isomer exhibiting a distinct oscillation period depending on the coher- powerful tool for the direct measurement of dynamics and conformational heterogeneity due to its high spatial and temporal ently excited vibrational mode. The proximity of the NO2 and CH3 moieties in 2-NT also enable a hydrogen atom transfer resolution. This technique can be applied to the study of fast, protein side-chain motions by site-specifically incorporating reaction in the 2-NT cation that proceeds within ∼ 20 − 60 fs and preserves the initially prepared vibrational coherence, unnatural amino acids with frequency-resolved absorptions in the “transparent frequency” region (1800 - 2500 cm−1). For which demonstrates that coherent vibrational dynamics can continue following an intramolecular rearrangement reaction. example, cyanophenylalanine (CNPhe) can be introduced in a protein in place of a native Tyr or Phe with minimal perturbation to the native protein structure. In this study, CNPhe was introduced in three distinct locations on the binding surface of the protein, plastocyanin (Pc) to investigate how the local environments of the chosen sites were impacted by the binding of its electron transfer partner, cytochrome f (cyt f ). The data suggests the Pc-cyt f complex has a highly mobile interface, supporting the model of a highly populated encounter complex. This study highlights the potential of 2D IR spectroscopy to reveal new biological insights of dynamic protein complexes and further demonstrates 2D IR spectroscopy as a routine measurement of protein dynamics.

TF02 8:48 – 9:03 PROBING VIBRATIONAL WAVE PACKETS IN ORGANOPHOSHOROUS MOLECULES USING FEMTOSECOND TIME-RESOLVED MASS SPECTROMETRY

DERRICK AMPADU BOATENG, KATHARINE MOORE TIBBETTS, Chemistry, Virginia Commonwealth TF04 9:24 – 9:39 University, Richmond, VA, USA. CONTROLLING DISSOCIATIVE DOUBLE IONIZATION OF ETHANE WITH ELLIPTICAL POLARIZED STRONG Organic phosphates and phosphonates share a basic structure with organophoshorous chemical warfare agents and cel- FIELDS lular components such as DNA. To understand ultrafast nuclear dynamics in isolated organic phosphates and phosphonates, Femtosecond Time Resolved Mass Spectrometry (FTRMS) was employed. FTRMS applies the pump-probe technique with GIHAN BASNAYAKE, Chemistry, Wayne State University, Detroit,, MI, USA; DUKE A. DEBRAH, Chemistry, mass spectrometric detection. In our experiment an ionizing 1014 Wcm−2, 1500 nm, 18 fs pump and a non-ionizing 1013 W Wayne State University, Detroit, MI, USA; WEN LI, Department of Chemistry, Wayne State University, Detroit, cm−2, 800 nm, 25 fs probe pulse were used. Experiments were performed on four related compounds: dimethyl methylphos- MI, USA. phonate (DMMP), diethyl methylphosphonate (DEMP), diisopropyl methylphosphonate (DIMP) and trimethyl phosphate (TMP). The yields of parent molecular ions generated by the pump pulse exhibited ultrafast oscillations with the period de- Laser control of chemical reactions has been a hot topic in recent years. Ethane, which has several dissociative double pending on the parent molecule. These oscillations indicate the presence of a vibrational wave packet that is excited upon ionization channels under strong laser fields has been subjected to intense investigation. With the aid of newly developed ionization. In DMMP, a well resolved peak of 45 fs (732 ± 28 cm−1) was observed with a weak feature at 610-650 cm−1, coincidence detection imaging system, we demonstrate that the branching ratios of dissociative double ionization channels of while DIMP exhibits bimodal oscillation with frequencies of 554±28 and 670-720 cm−1. Oscillations for DEMP were barely ethane can be controlled by varying the ellipticity of the intense ultrashort laser pulses. The Methyl ion formation channel and visible due to rapid decay. The high- and low- frequency oscillations in DMMP and DIMP were assigned to coherent excita- proton formation channel show a significant yield changes, producing the highest and lowest at ellipticity of 0.6 respectively. tion of O-P-O bend and P-C stretching respectively based on DFT calculations. Bimodal oscillations at 770 and 880 cm−1 in We attribute such a control to both angle dependent ionization and intensity dependent ionization to excited dication states. TMP were also observed and are tentatively assigned to the symmetric and asymmetric P-O stretching modes. These results suggest that this group of compounds exhibits similar coherent vibrational excitation upon ionization. These results may have applications to development of new organophosphorous chemical warfare agent detection and destruction techniques based on the coherent control and may point to reaction pathways in organophosphorous compounds of biological relevance. 100 101

TF05 9:42 – 9:57 TF07 10:54 – 11:09 UF-CRDS: A PULSED UNIFORM FLOW APPARATUS WITH CW-CAVITY-RINGDOWN SPECTROSCOPY PYROLYSIS OF ETHYL ESTERS IN A MICRO-REACTOR

NICOLAS SUAS-DAVID, SHAMEEMAH THAWOOS, ARTHUR SUITS, Department of Chemistry, Univer- CORY ROGERS, Department of Mechanical Engineering, University of Colorado Boulder, Boulder, CO, USA; sity of Missouri, Columbia, MO, USA. JESSIE P PORTERFIELD, Radio and Geoastronomy Division, Harvard-Smithsonian Center for Astrophysics, Cambridge, MA, USA; JOHN W DAILY, Department of Mechanical Engineering, University of Colorado Boul- We introduce a new apparatus in which a high-performance pulsed supersonic uniform flow from a Laval nozzle is der, Boulder, CO, USA; BARNEY ELLISON, Department of Chemistry and Biochemistry, University of Col- coupled with a continuous wave cavity ringdown spectroscopy (cw-CRDS). This approach is related to the CRESUa technique orado, Boulder, CO, USA; NICOLE LABBE, Department of Mechanical Engineering, University of Colorado, developed in France to study reaction kinetics at low temperature. A related system developed in our group in which chirped- Boulder, CO, USA. pulse microwave spectroscopy is coupled to a pulsed Laval flow has successfully demonstrated its investigative capability of isomer-specific product branching in reactions and photodissociation at temperatures as low as 22 Kb. The pulsed uniform The nascent steps in the pyrolysis of ethyl esters have been studied in a set of heated micro-reactors. We have examined c flow is produced by means of a high throughput piezoelectric stack valve combined with a Laval nozzle. At present, we the thermal decomposition of ethyl propionate, CH3CH2COOCH2CH3, a model for biofuels. The micro-reactors are small employ two machined aluminum nozzles (for carrier gases He and Ar at temperatures around 25 K), and numerous in-house (roughly 1 mm ID x 3 cm long) silicon carbide tubes; transit times through the reactors are about 100 μsec. Temperatures in 3D printed nozzles. The 3D printed nozzles are designed using a Matlab program developed in-house, which allows us to the micro-reactors can be as high as 1700 K and pressures are typically 100 Torr. The products of pyrolysis are identified by a create supersonic uniforms flows with different carrier gases at various temperature and densities. These nozzles are validated combination of 118.2 nm photoionization mass spectrometry and matrix isolation infrared absorption spectroscopy. We find −−→ + experimentally as well as theoretically using a computational fluid dynamics program, OpenFOAM. there are two major pathways for ethyl propionate decomposition. These are: CH3CH2COOCH2CH3 CH3CH2COOH − −−→ − − + The current configuration can probe the pulsed uniform flow either by cw-CRDS, operated in the near infrared region, CH2−CH2 and CH3CH2COOCH2CH3 CH3CH−C−O CH3CH2OH. The nascent pyrolysis products undergo further, or laser-induced fluorescence as in the traditional CRESU approach. The cw-CRDS spectrometer consists of a high finesse extensive fragmentation in the reactor. optical cavity (F 200000) which is composed of two high reflective plano-concave mirrors (R 99.9988%) leading to an empty cavity decay constant of 160 μs. We adopt a modified version of the timing strategy which was reported by Hippler M. et ald in order to probe reactants of bimolecular reactions formed from photolysis. We will present our first low temperature kinetics experiments performed with this apparatus including reaction of CN (v=1) with alkenes probed by cw-CRDS.

aSims,I., Queffelec, J.L., Defrance,A., Rebrion-Rowe,C., Travers,D., Bocherel, P., Rowe, B., and Smith, I.W.M., J. Chem. Phys. 100 (6), 4229-4241 (1994). bBroderick, B.M., Suas-David, N., Dias, N., and Suits, A.G., Phys. Chem. Chem. Phys. 20 (8), 5517-5529 (2018). cOldham, J.M., Abeysekera, C., Joalland, B., Zack, L.N., Prozument, K., Sims, I.R., Park, G.B., Field, R.W., and Suits, A.G., J. Chem. Phys. 141 (15), 154202 (2014). dHippler, M., and Quack, M., M Hippler, et.al, Chem. Phys. Lett. 314 (3), 273-281 (1999).

TF08 11:12 – 11:27 TF06 10:00 – 10:15 NUCLEAR SPIN CONVERSION OF PROPYNE IN SOLID PARAHYDROGEN PRODUCT BRANCHING AND LOW TEMPERATURE REACTION KINETICS BY CHIRPED-PULSE FOURIER TRANSFORM MM-WAVE SPECTROSCOPY IN A PULSED UNIFORM SUPERSONIC FLOW AARON I. STROM, DAVID T. ANDERSON, Department of Chemistry, University of Wyoming, Laramie, WY, USA. NURESHAN DIAS, RITTER KRUEGER, NICOLAS SUAS-DAVID, ARTHUR SUITS, BERNADETTE M. BRODERICK, Department of Chemistry, University of Missouri, Columbia, MO, USA. We report observations of propyne (H3CCCH) nuclear spin conversion (NSC) in solid parahydrogen (para-H2)at1.7 K via high-resolution matrix isolation infrared spectroscopy. A rapid vapor deposition technique is used to codeposit room The CRESU technique (French acronym for “reaction kinetics in uniform supersonic flows”) has been applied with temperature H3CCCH and precooled para-H2 gas streams onto a cold substrate maintained below 2.4 K with flow rates that great success in the past two decades to study the kinetics of reactions at low temperatures. In this approach, a uniform low ensure the expeditious growth of monomer-doped solids. This study will focus on the ν2 and ν6 modes of propyne in the temperature flow is produced via a Laval nozzle expansion giving a wall-less reactor at constant pressure and low temperature. methyl C–H stretching region near 3.4 μm, which correspond to parallel and perpendicular rovibrational bands, respectively. Product detection in that work has been either with laser-induced fluorescence directly in the flow or vacuum ultraviolet For both bands, temporal changes in peak intensities are detected that are characteristic of NSC. In this way, NSC can be used photoionization after sampling. We have recently combined low temperature Laval flows with broadband mm-wave detection to assign peaks originating from K=0 (A, I=3/2) and K=1 (E, I=1/2) levels, even when absorptions are strongly overlapping. (chirped-pulse/uniform flow or “CPUF”) to study product branching in photodissociation and reaction.a Because chirped- Based on these observations, the fine structure observed in these two bands can be assigned to K-rotational structure. At these pulse microwave detection requires monitoring the free induction decay on the timescale of microseconds, it cannot be temperatures, the K=1 rotational state should not be populated without nuclear spin restrictions on the total wavefunction. employed at the high densities we achieve in the flows. We have used two approaches to overcome this limitation. In one, we Thus, the slow NSC process allows the K=1 level population to be partially trapped in the low-temperature solid. The used a “quasi-uniform” flow in which an unoptimized Laval flow was followed by a second expansion to lower temperature observation of this NSC process means that the K rotational quantum number is at least partially conserved, indicating bc and density. Detailed fluid dynamics simulations allow us to understand the temperature and density throughout that flow. H3CCCH rotates about its symmetry axis in the para-H2 matrix. The extracted time constant for NSC (τ=270(10) min) is a b c d Product branching can be measured under these conditions but not kinetics, as the conditions vary throughout the flow. within an order of magnitude of measurements for other methyl-rotors (H3CX; X = H; F; OH; C(O)CH = COHCH3 ) d Recently we have implemented airfoil sampling of an optimized flow. This allows us to study low temperature kinetics as in trapped in para-H2 matrices, however, this is the fastest rate of relaxation measured to date. These findings are discussed in CRESU, but with the power of broadband mm-wave spectroscopy. Recent results for several systems relevant to chemistry in light of accepted models for NSC and the various rovibrational selection-rules for the above-mentioned molecules. cold molecular clouds and planetary atmospheres will be presented using both the quasi-uniform flow and airfoil sampling. aY. Miyamoto, M. Fushitani, D. Ando, T. Momose, J. Chem. Phys. 128, 114502 (2008). b aOldham, J. M.; Abeysekera, C.; Joalland, B.; Zack, L. N.; Prozument, K.; Sims, I. R.; Park, G. B.; Field, R. W.; Suits, A. G. 2014, 141, 154202 Y.-P. Lee, Y.-J. Wu, J.T. Hougen, J. Chem. Phys. 129, 104502 (2008). c bDias, N.; Joalland, B.; Ariyasingha, N. M.; Suits, A. G.; Broderick, B. M. The Journal of Physical Chemistry A 2018, 122, 7523-7531. Y.-P. Lee, Y.-J. Wu, R.M. Lees, L.-H. Xu, J.T. Hougen, Science 311, 365 (2006). d cBroderick, B. M.; Suas-David, N.; Dias, N.; Suits, A. G. Physical Chemistry Chemical Physics 2018, 20, 5517-5529. R.R. Lozada-Garcia, J. Ceponkus, M. Chevalier, W. Chin, J.-M. Mestdagh, C. Crepin,´ Angew.Chem.Int.Ed.51, 6947 (2012). dSoorkia, S.; Liu, C.-L.; Savee, J. D.; Ferrell, S. J.; Leone, S. R.; Wilson, K. R. Review of Scientific Instruments 2011, 82, 124102.

Intermission 102 103 TG. Mini-symposium: Astrochemistry and Astrobiology in the age of ALMA TF09 11:30 – 11:45 Tuesday, June 18, 2019 – 1:45 PM THE TEMPERATURE DEPENDENCE OF THE H + N2O REACTION IN SOLID HYDROGEN Room: 116 Roger Adams Lab FREDRICK M. MUTUNGA, KELLY M. OLENYIK, AARON I. STROM, KAYCEE L. FILLMORE, DAVID T. ANDERSON, Department of Chemistry, University of Wyoming, Laramie, WY, USA. Chair: Isabelle Kleiner, CNRS et Universites´ Paris-Est et Paris Diderot, Creteil,´ France In the late 1960s Andreev and Lifshitz predicted that at sufficiently low temperatures defects in quantum crystals such as solid parahydrogen should move freely through the crystal possessing the property of superfluidity.a The hydrogen atom (H-atom) is an ideal candidate for such a defect owing to its small mass and neutral charge. In 2013 our group published a communicationb on the kinetics of the H + N2O reaction in solid parahydrogen that showed an anomalous temperature dependence. In these studies we generate the H-atoms as byproducts of the in situ photodissociation of N2O and monitor the subsequent reaction kinetics using rapid scan FTIR. Specifically, if we photolyze N2O doped parahydrogen solids with a short INVITED TALK duration of 193 nm UV radiation at 4.3 K, we observe little to no reaction; however, if we then slowly reduce the temperature TG01 1:45 – 2:15 of the sample after photolysis we observe an abrupt onset to the reaction at temperatures below 2.4 K. This change in the MOLECULAR DISCOVERY ACROSS THE ALMA BANDS: FROM SALTY DISKS TO COMPLEX MOLECULES AT reaction kinetics is fully reversible with temperature. We have subsequently improved our experimental apparatus such that 900 GHz we can record the sample temperature with millisecond time resolution while we measure the reaction kinetics using FTIR spectroscopy. We have now performed a number of additional kinetic experiments at constant temperatures of 1.5 K, 4.0 K, BRETT A. McGUIRE, NAASC, National Radio Astronomy Observatory, Charlottesville, VA, USA. and intermediate temperatures within the range from 1.5 to 4.0 K. These measurements have shown that the reaction yield changes dramatically over this temperature range, but the kinetic rate coefficients do not change significantly. The remarkable The Atacama Large Millimeter/sub-millimeter Array (ALMA) provides a view of our molecular universe with unprece- change in the reaction kinetics with temperature is not as abrupt as originally thought, but now has been reproduced under a dented sensitivity and resolution over more than 850 GHz in bandwidth from 84 – 950 GHz. In this talk, I will cover three variety of conditions. This strange behavior is intimately linked to the motion and reactivity of H-atoms in solid parahydrogen recent results that showcase not only ALMA’s power to probe interstellar chemical evolution, but also the critical role of and the most recent experiments and analysis will be presented. laboratory molecular spectroscopy efforts in interpreting ALMA observations. At lower frequencies, I will discuss our recent detections of the extraordinarily vibrationally excited inorganic salts NaCl and KCl in the disk of Orion Src I, which may aA. F. Andreev and I. M. Lifshitz, Sov. Phys. JETP. 29, 1107-1113 (1969). prove to be a unique, and much needed, probe of embedded disks around high-mass protostars. Moving up both in frequency bF.M. Mutunga, S.E. Follett, D.T. Anderson, J. Chem. Phys. 139, 151104-4 (2013). and complexity, I will highlight our detection of methoxymethanol (CH3OCH2OH) in the high-mass star-forming region NGC 6334I in very high abundance that was directly enabled by complementary laboratory spectroscopy work. Finally, I will TF10 11:48 – 12:03 discuss the first broadband line survey conducted with ALMA at Bands 9 and 10, again toward NGC 6334I. I will comment ULTRACOLD CHEMICAL REACTIONS OF KRb MOLECULES on not only the power and quality of high-frequency observations with ALMA but also the need for renewed laboratory efforts at these frequencies, as highlighted by glycolaldehyde (HC(O)CH2OH) and ethylene glycol ((CH2OH)2). DAVID GRIMES, YU LIU, MING-GUANG HU, ANDREI GHEORGHE, KANG-KUEN NI, Department of Chemistry and Chemical Biology, Harvard University, Cambridge, MA, USA.

Our goal is to understand the details of the quantum dynamics of chemical reactions that take place at ultracold (< 1 μK) temperatures. These dynamics fundamentally determine both the products of the chemical reaction and their quantum states. We have constructed an apparatus that combines techniques from atomic physics and physical chemistry in order to prepare reactant KRb molecules in a single quantum state and detect product molecule quantum state distributions with a TG02 2:21 – 2:36 → highly sensitive ionization detection method. We apply this approach to the chemical reaction KRb + KRb K2 +Rb2 in THE LABORATORY ROTATIONAL STUDY OF METHYL ISOCYNATE the ultracold regime. ZBIGNIEW KISIEL, ON2, Institute of Physics, Polish Academy of Sciences, Warszawa, Poland; LUCIE KOLESNIKOVA´ , ELENA R. ALONSO, Grupo de Espectroscopia Molecular, Lab. de Espectroscopia y Bioespectroscopia, Unidad Asociada CSIC, Universidad de Valladolid, Valladolid, Spain; JOSE CERNICHARO, Molecular Astrophysics, ICMM, Madrid, Spain; J.-C. GUILLEMIN, Ecole Nationale Superieure` de Chimie de Rennes, Univ. Rennes, Rennes, France;JOSE´ L. ALONSO, Grupo de Espectroscopia Molecular, Lab. de Espec- troscopia y Bioespectroscopia, Unidad Asociada CSIC, Universidad de Valladolid, Valladolid, Spain.

Methyl isocyanate (CH3NCO) is one of the most abundant species detected on the surface of the 67P/Churyumov- Gerasimenko comet.a It has also been discovered in space towards the Orion clouds where a large number of rotational lines arising from energy levels with K ≤ 3 were reported.b In the present work, Stark-modulation spectroscopy was used to record the room temperature rotational spectrum of CH3NCO in the spectral region from 32 to 90 GHz and to assign rotational transitions up to K = 10. These new assignments were subsequently followed up to 364 GHz. Also, first laboratory 13 13 measurements between 50 and 300 GHz have been performed for CH3N CO and CH3NCO isotopologues. Updated extensive line lists along with new sets of spectroscopic parameters provided in this work meet the needs for further detections of CH3NCO in space.

aGoesmann, F., Rosenbauer, H., Bredehoft, J.H., et al. 2015, Science, 349, aab0689. bCernicharo, J., Kisiel, Z., Tercero, B., et al. 2016, A&A, 587, L4. 104 105

TG03 2:39 – 2:54 TG05 3:15 – 3:30

LARGE AMPLITUDE MOTION EFFECTS IN THE TPES SPECTRUM OF METHYL ISOCYANATE CH3NCO SUBMILLIMETER WAVE SPECTROSCOPY FOR ISM: IMINES WITH INTERNAL ROTATION

O. J. HARPER, B. GANS, S. BOYE-P´ ERONNE,´ L. H. COUDERT, Institut des Sciences Moleculaires´ d’Orsay, L. MARGULES` ,R.A.MOTIYENKO,UMR 8523 - PhLAM - Physique des Lasers Atomes et Molecules,´ Univer- Universite´ Paris-Sud, Orsay, France; J.-C. LOISON, Institut des Sciences Moleculaires,´ UniversitedeBor-´ sity of Lille, CNRS, F-59000 Lille, France; V. ILYUSHIN, OLGA DOROVSKAYA, Radiospectrometry Depart- deaux, Talence, France; G. A. GARCIA, DESIRS beamline, Synchrotron SOLEIL, Gif-sur-Yvette, France;J.-C. ment, Institute of Radio Astronomy of NASU, Kharkov, Ukraine; ANTHONY REMIJAN, BRETT A. McGUIRE, GUILLEMIN, ENSC, Univ. Rennes, Rennes, France. NAASC, National Radio Astronomy Observatory, Charlottesville, VA, USA; J.-C. GUILLEMIN, UMR 6226 CNRS - ENSCR, Institut des Sciences Chimiques de Rennes, Rennes, France. Methyl isocyanate is a non-rigid quasi-symmetric top molecule displaying a torsion of its methyl group and a large amplitude CNC bending mode.a The torsion is nearly free as the hindering barrier is only 20 cm−1. The barrier to linearity, The aldimines are important to understand amino acids formation process as they appear in reaction scheme of Strecker- also very low, is on the order of 920 cm−1. Although the a-type transitions of methyl isocyanate have already been recorded type synthesis. It seems reasonable to propose syntheses in the solid phase but the formation process is not clearly established. up to the submillimeter wave domain,b spectroscopic information is still lacking, especially concerning the cation. The number of imines and amines detected in the interstellar medium is limited, mainly due to lack of spectroscopic data. Threshold photoelectron spectroscopy has been used to obtain spectroscopic information on the cationic species We present here the studies of ethanimine (CH3CHNH) and methylimino-acetonitrile (CH3N=CHCN). Both of them have + −1 (CH3NCO ) of methyl isocyanate. The spectrum recorded from 84000 to 94000 cm (10.4 to 11.6 eV) using VUV syn- has two isomers E and Z with E one being the most stable. These molecules represent a particular case where a quite high chrotron radiation displays several sharp features superimposed on a broad feature spanning nearly 8000 cm−1. As shown by (570 and 714 cm−1 respectively) internal rotation barrier is combined with relatively a high ρ value (close to 0.3) making the ab initio calculations carried out in this work, the ground electronic state of the cation is doubly degenerate and is split analysis of the spectra rather delicate. The fits were performed using a version of RAM36 codea which includes the treatment into a lower X + and an upper A+ substate by vibronic couplings. The ground electronic state of the neutral and the X + of the nuclear quadrupole hyperfine structure. Ethanimine was detected already in ISMb, but the spectrosocpic analyses were + c,d substate of the cation are characterized by similar values of the methyl group internal rotation barrier. As for the A substate limited to low Ka values . In the current study we significantly extend the rotational quantum number coverage for this of the cation, a much larger value shifted by π/3 was calculated. molecule. Accounting for the two large amplitude motions and for the overall rotation,a a calculation of the rovibronic energies of The spectroscopic results for both molecules and searches of methylimino-acetonitrile in ISM will be presented. the neutral and the cationic species is in progress and should allow us to model the TPES spectrum. This calculation relies on This work was supported by the CNES and the Action sur Projets de l’INSU, PCMI. c Gaussian quadrature to treat the singularity at the linear configuration. The strong dependence on the methyl group internal a a Ilyushin, V.V. et al;J. Mol. Spectrosc. 259, (2010) 26 rotation barrier on the CNC bending angle is also taken into account. In the talk, the results of the rovibronic energies bLoomis, R. A.; et al. ApJ. Lett. 765,(2013) L9 calculation will be reported and the experimental TPES spectrum will be compared to the theoretical one. cLovas, F. J.; et al. J. Chem. Phys. 72, (1980) 4964 dMelli A.; et al. ApJ 855, (2018) 123 aKre¸glewski, J. Molec. Spectrosc. 105 (1984) 8; and Koput, ibid. 106 (1984) 12 bKoput, J. Molec. Spectrosc. 115 (1986) 131; and Cernicharo et al., A&A 587 (2016) L4 cCoudert, Gans, Holzmeier, Loison, Garcia, Alcaraz, Lopes, and Roder,¨ J. Chem. Phys. 149 (2018) 224304 Intermission

TG06 4:09 – 4:24 THE NANOCOSMOS GAS CELL: A BROADBAND FOURIER TRANSFORM MILLIMETERWAVE SPECTROMETER BASED ON RADIO ASTRONOMY RECEIVERS

CELINA BERMUDEZ´ , CARLOS CABEZAS, Instituto de Fisica Fundamental, CSIC, Madrid, Spain;ISABEL TANARRO, JOSE´ LUIS DOMENECH,´ VICTOR JOSE HERRERO, Molecular Physics, Instituto de Estructura TG04 2:57 – 3:12 de la Materia (IEM-CSIC), Madrid, Spain; JUAN DANIEL GALLEGO, PABLO DE VICENTE, FELIX´ TER- MICROWAVE-WAVE SPECTROSCOPY OF 5-METHYL HYDANTOIN CERO, JOSE´ ANTONIO LOPEZ´ PEREZ,´ Centro Astronomico´ de Yebes, Observatorio Astronomico´ Nacional, Yebes, Guadalajara, Spain; JOSE CERNICHARO, Instituto de Fisica Fundamental, CSIC, Madrid, Spain. HIROYUKI OZEKI,MINAMIAWATSU,Department of Environmental Science, Toho University, Funabashi, Japan;KAORIKOBAYASHI,Department of Physics, University of Toyama, Toyama, Japan. We present the first spectroscopic results on a newly built broadband Fourier transform millimeterwave spectrometer for the laboratory which employs the same detection system as that present in radio-telescopes. The spectrometer is equipped Hydantoin (Imidazolidine-2,4-dione, C3H4N2O2 is a five-membered heterocyclic compound, and has been regarded as with Q-band (31.5-50GHz) and W-band (72-116GHz) receivers, very sensitive to the rotational emission of the molecules a direct precursor of glycine, the simplest amino acid. The molecule was detected in carbonaceous chondrites together with present in a one meter Gas Cell. The technique provides large instantaneous bandwidth, spectral purity, and a linear de- several kinds of amino acids.a We have measured pure rotational spectrum of the molecule in its ground and vibrationally pendence of the signals with the partial pressure so that it is perfectly suited for high resolution emission spectroscopy of excited states, and have provided the molecular line frequency list in the millimeter-wave region for astronomical search.b molecules of astrophysical importance. The full description of the cell can be found in the literaturea,b. 5-methyl hydantoin is the simplest chiral molecule among hydantoins, because either of the hydrogen atoms bonded to the In the present contribution we will show the capabilities of the spectrometer. The Gas Cell has been initially tested with C5 position of the five-membered ring is asymmetrically substituted. The molecule becomes a direct precursor of alanine, the molecules whose rotational spectrum was well known (CH3CN, OCS, SO2. . . ). High accuracy measurements of the frequen- simplest chiral amino acid. We have tried to observe pure rotational spectrum of 5-methyl hydantoin in the millimeter-wave cies (38KHz) and intensities (in K) can also be determined using our new instrument. Subsequently, Gas Cell experiments to sub-millimeter-wave region. Guided with quantum chemical calculation, several spectral lines can be assigned to b-type have been devoted to the study the rotational spectra of molecules of astrochemical interest whose millimeterwave spectrum transitions. remains unknown. Among these molecules, the formamide derivatives and dinitriles are very attractive because they are

aA. Shimomiya, and R. Ogasawara, Orig. Life Evol. Biosph. 32, 165 (2002) candidates to be found in the space and they present low-energy excited vibrational states that can also contribute to the large bH. Ozeki, R. Miyahara, H. Ihara, S. Todaka, K. Kobayashi, and M. Ohishi, Astron. Astrophys. 600 A44 (2017). number of unidentified lines in the millimeter and submillimeter wave surveys.

aI. Tanarro et al. 2019, A&A,609,A15 bJ. Cernicharo et al., 2019, A&A 106 107

TG07 4:27 – 4:42 TG09 5:03 – 5:18 + THE NANOCOSMOS GAS CELL AS A TOOL FOR SPECTROSCOPY: THE MILLIMETERWAVE SPECTRUM OF N- FORMATION OF THE ALMA MOLECULE HOCH2CN AND RELATED SPECIES FROM THE REACTION OF C ETHYLFORMAMIDE WITH HCN AND HNC IN ICY GRAIN MANTLES

CELINA BERMUDEZ´ , CARLOS CABEZAS, Instituto de Fisica Fundamental, CSIC, Madrid, Spain;JUAN DAVID E. WOON, Department of Chemistry, University of Illinois at Urbana-Champaign, Urbana, IL, USA. DANIEL GALLEGO, JOSE´ MANUEL HERNANDEZ, Centro Astronomico´ de Yebes, Observatorio As- + tronomico´ Nacional, Yebes, Guadalajara, Spain; ISABEL TANARRO, JOSELUISDOM´ ENECH,´ VICTOR Density functional theory cluster calculations indicate that the intermediate HOCHNC readily forms when C reacts JOSE HERRERO, Molecular Physics, Instituto de Estructura de la Materia (IEM-CSIC), Madrid, Spain; with HCN embedded in the surface of an icy grain mantle. Subsequent H addition to HOCHNC yields the iscyano compound BELEN´ TERCERO, OAN-IGN, Observatorio Astronomico´ Nacional, Madrid, Spain; ANA CRISTINA SO- HOCH2NC. There is enough energy from the H addition for HOCH2NC to isomerize to HOCH2CN (glycolonitrile), an RIA, Analisis´ Instrumental y Qu´ımica Ambiental, CSIC, Madrid, Spain;ROSALEBRON,´ JESUS´ EDUARDO important prebiotic molecule that was recently detected with ALMA observations toward the solar-type protostellar source QUINTANILLA, Instituto Qu´ımica-F´ısica Rocasolano, CSIC, Madrid, Spain; JOSE CERNICHARO, Instituto IRAS 16293-2422 B by Zeng et al. [MNRAS 2019, 484, L43]. It was found that H can also add to HOCHNC to form + de Fisica Fundamental, CSIC, Madrid, Spain. HOCHNCH without a barrier. The analogous reactions of C with HNC in ice will also be discussed. Vibrational spectra of the various ice-bound reactants, intermediates, and products will be presented. The calculations were performed with B3LYP Several molecules containing a peptidic bond in their structure such as formamide (HCONH2) and some derivative using aug-cc-pVDZ sets on C, N, and O and cc-pVDZ sets on H. a compounds have been already found in the interstellar medium . In case of N-ethylformamide (HCONHCH2CH3), only the microwave spectrum is known up to 20 GHz hence the rotational constants for the conformers found are not accurate enough to detect the molecule in the interstellar medium. In the present work we have employed the Nanocosmos Gas Cell spectrometer to record the millimeterwave spectrum of N- ethylformamide. The recently built broadband Fourier transform millimeterwave spectrometerb employs radio astronomical receivers for the Q-band (31.5-50GHz) and W-band (72-116GHz) to detect the thermal emission of the molecules in the Gas Cell chamber. The aim consists on establishing the concept of Nanocosmos Gas Cell as a new tool for high resolution broadband molecular spectroscopy in the millimeterwave region. In this study not only the ground state but also a higher energy conformer and some vibrational excited states have been identified and analyzed. The rotational constants will be used to search for this molecule in the space.

aR.H. Rubin et al., 1971, ApJL, 169, L39, and see e.g. A.J. Remijan et al., 2014, ApJ, 783, 77 bI. Tanarro et al., 2018, A&A, 609, A15 and J. Cernicharo et al., 2019, A&A

TG08 4:45 – 5:00 EXTENDED ANALYSIS OF THE ROTATIONAL SPECTRUM OF METHOXYISOCYANATE IN THE GROUND AND LOWEST EXCITED VIBRATIONAL STATES

R. A. MOTIYENKO, UMR 8523 CNRS - Universite´ de Lille, Laboratoire PhLAM, Villeneuve d’Ascq, France;A. PIENKINA, Laboratoire de Physico-Chimie de l’Atmosphere,` Universite´ du Littoral Coteˆ d’Opale, Dunkerque, France;L.MARGULES,` UMR 8523 CNRS - Universite´ de Lille, Laboratoire PhLAM, Villeneuve d’Ascq, France; J.-C. GUILLEMIN, UMR 6226 CNRS - ENSCR, Institut des Sciences Chimiques de Rennes, Rennes, France.

Methoxyisocyanate, CH3ONCO is a methoxy derivative of isocyanic acid HNCO detected in the interstellar medium back in 1972a. Recent detections of methyl isocyanate, a methyl derivative of HNCO, towards Sgr B2(N)b, and in the c d Orion , as well as the detection of methoxymethanol motivated us to study the rotational spectrum of CH3ONCO as a candidate molecule for searches in the interstellar medium. The previously presented study of the rotational spectrum of methoxyisocyanatee showed the complexity of the problem owing to the large amplitude motion, a skeletal torsion along ON bond. The analysis revealed the existence of the ”ladder” Coriolis-type interactions between the ground and lowest skeletal torsional states. We present here the extension of the rotational spectrum analysis that includes new types of resonances as well as the assignment of new excited vibrational states of methoxyisocyanate. In particular, the inclusion of new resonances permitted to assign and fit within experimental accuracy high Ka transitions of the ground vibrational state. This work was supported by the CNES and the Action sur Projets de l’INSU, PCMI.

aSnyder, L.E. and Buhl, D. 1972, ApJ, 177, 619 bHalfen, D.T., Ilyushin, V.V. and Ziurys, L.M. 2015, ApJ, 812,L5 cCernicharo, J. et al. 2016, A&A, 587,L4 dMcGuire, B.M. 2017, ApJ 851, L46 (2017) ePienkina, A. et al. 2017, 72nd ISMS, WA03 108 109 TH. Mini-symposium: Non-covalent Interactions Tuesday, June 18, 2019 – 1:45 PM TH03 2:39 – 2:54 LOCAL MODE APPROACH TO THE CH STRETCH SPECTRA OF DINAPHTHYLETHANES Room: 100 Noyes Laboratory ANGELA ABLABERDIEVA, Department of Chemistry, University of Wisconsin–Madison, Madison, WI, USA; Chair: Anna Huff, University of Minnesota, Minneapolis, MN, USA DANIEL M. HEWETT, Department of Chemistry and Biochemistry, Old Dominion University, Norfolk, VA, USA; TIMOTHY S. ZWIER, Department of Chemistry, Purdue University, West Lafayette, IN, USA;EDWIN SIBERT, Department of Chemistry, University of Wisconsin–Madison, Madison, WI, USA.

Recent advances in conformer-specific ultracold gas-phase IR spectroscopy have enabled the examination of the CH stretch region by alleviating the extensive broadening observed in condensed-phase systems. Theoretical approaches to pre- TH01 INVITED TALK 1:45 – 2:15 diction of CH stretch IR spectra, however, remain challenging due to the influence of stretch-bend coupling in this region. SPECTROSCOPY OF JUPITER’S ATMOSPHERE: INSIGHTS FROM DFT AND AB-INITIO CALCULATIONS Here, we demonstrate the utility of local mode analysis in obtaining conformer-specific spectral assignments of mid-size organic molecules (20-40 atoms). Unitary transformations of the Hamiltonian from normal- to local-mode coordinates offer a JOSEPH S FRANCISCO, TAREK TRABELSI, Department of Earth and Environmental Science and Depart- practical method of investigation. In this study, three isomers of dinaphthylethane were examined using local mode analysis, ment of Chemistry, University of Pennsylvaina, Philadelphia, PA, USA. revealing insights into the preferred conformers of each. Electronic structure calculations indicate that gauche arrangements of the naphthyl rings are lower in energy than other possible configurations; these results also suggest that the experimentally- Despite several space mission and astronomical observation made from earth, the structure, color and mode of formation observed spectra are generated by gauche conformers. Unexpectedly, these findings indicate that through significant van der of Jupiter planet and other Jovian planet remain largely unknown. Understanding the atmosphere, haze and the colors of Waals interactions, the naphthyl rings are able to overcome the steric strain resulting from their gauche configuration. In these planets, especially the great red spot (GRS) of Jupiter and its belts are still a big challenge for both experimenters and addition, one experimentally-observed spectrum contains unique features that have encouraged us to continue developing our theorists. Jupiter’s colors range from blue to orange with some green regions. The most important chemical components that model in an exploration of possible interpretations. The insights we have gained using local mode analysis serve as encour- are responsible for the coloring of Jupiter and other Jovian planets are mainly CH4, NH4SH, H2O and NH3 [1-3]. Although aging indications that this methodology is a promising candidate for extension to more complicated systems, including those an explanation for the color of Jupiter have been suggested to involve these species or other related molecules arise from the containing additional functional groups such as OH and NH stretches. interaction between these species in gas phase. In this report, we present our studies on the color of Jupiter. We have examined the electronic structure, stability infra-red and UV-Vis spectroscopy of NH4SH and other related molecules in crystalline and gas phase using Density Functional Theory (DFT) and ab-initio methods, are we report new insights from the spectroscopy NH4SH in explaining the different color regions of Jupiter. References: 1.Roman, M.T., Banfield, D., Gierasch, P.J., Icarus, 225, 93 (2013). 2.Atreya,S.K et al., Planet Space Sci., 47, 1243 (1999). 3.Weidenschilling, S.J., Lewis, J.S., Icarus 20, 465 (1973).

TH04 2:57 – 3:12 TH02 2:21 – 2:36 A PATH FROM GAS TO LIQUID: DEVELOPMENT OF MODEL HAMILTONIANS FOR CONDENSED PHASE LOCAL UNCOVERING A NEW CLASS OF REACTIONS IN THE ATMOSPHERE: SN2-TYPE SUBSTITUTION REACTIONS MODE IR SPECTRA VIA BENZENE (Bz) AND Bz2 OF NITROGEN OXIDES AND SEAWATER ZACHARY DYOTT, Department of Chemistry, University of Wisconsin-Madison, Madison, WI, USA;EDWIN LAURA M McCASLIN, Department of Chemistry, University of California Irvine, Irvine, CA, USA;MARK SIBERT, Department of Chemistry, University of Wisconsin–Madison, Madison, WI, USA. JOHNSON, Department of Chemistry, Yale University, New Haven, CT, USA; R. BENNY GERBER, Fritz Haber Center for Molecular Dynamics and Institute of Chemistry, The Hebrew University of Jerusalem, Jerusalem, Condensed-phase systems represent a vast swath of chemical problems that are of biological and atmospheric interest. Israel. Force fields for simulations of these liquid phases need to be able to model intermolecular interactions accurately. Moreover, reliable potentials for spectroscopic calculations need to reproduce site energies and molecular properties, as well as predict Recent studies indicate that nitrogen oxide species in the atmosphere, including N2O5 and ONONO2, undergo a new class fluctuations in molecular coupling appropriately. A local mode approach to the calculation of IR spectra of condensed phase a,b,c of SN 2-type substitution reactions when in contact with seawater and sea spray aerosols. The reactions of atmospheric systems of CH stretches will be taken. This is justified because solutions of only CH stretches tend to exhibit less correlated nitrogen oxides with seawater play many integral roles in regulating levels of O3,OH,NOx,andCH4, thus directly affecting network behavior than solutions of mixed CH/XH (X=O,N) stretch solvents due to weaker intermolecular forces. In an effort radiative forcing and global climate. However, the effect of the number of water molecules on the mechanisms for this to understand solvent effects in the condensed phase, previously developed model gas-phase Hamiltonians will be extended new group of SN 2-type reactions of nitrogen oxides and the competition of these processes with hydrolysis have not yet to describe liquid CH stretch systems. As a first step, benzene will be investigated due to its high degree of symmetry been characterized. Here we present the mechanisms and timescales of SN 2-type substitution and hydrolysis reactions of and availability of force fields that describe its intermolecular interactions. Benzene represents a technical challenge for − − N2O5 with seawater in the cluster series N2O5 +Cl +nH2O (n=1-5). Previous studies of the cluster N2O5 +Cl +H2O vibrational spectroscopy due to the presence of a Fermi triad in its CH stretch IR spectrum. By incorporating these couplings provide deep insights into the local behavior of these systems.c The presented studies of this cluster with water molecules into the model Hamiltonian, it will be possible to consider solvent effects on the IR spectrum of the noncovalently bound added one-by-one allows for a detailed understanding of the effects of a solvation shell as it is built, providing a connection benzene dimer. Extension of the dimer model to the condensed phase will allow for discussion of other relevant spectra of between the behavior of these small clusters and atmospherically relevant systems. Vibrational spectroscopic signatures of benzene, especially its vibrational sum-frequency generation (VSFG) spectrum. key intermediates are discussed and compared to recent and ongoing experiments.a

aP. J. Kelleher, F. S. Menges, J. W. DePalma, J. K. Denton, M. A. Johnson, G. H. Weddle, B. Hirshberg, R. B. Gerber, J. Phys. Chem. Lett. 8, 4710 (2017). bR. B. Gerber, L. McCaslin, N. V. Karimova, Faraday Discuss. (Accepted). cL. M. McCaslin, M. A. Johnson, R. B. Gerber, (In review)

Intermission 110 111

TH05 3:51 – 4:06 TH07 4:27 – 4:42 THEORETICAL STUDY OF SURFACE-ENHANCED RAMAN SPECTRA OF WATER AND IONIC COMPLEXES IN THE PREDICTION AND OBSERVATION OF VDW COMPLEXES OF HIGHLY VIBRATIONALLY EXCITED CS AND ELECTROCHEMICAL INTERFACES SIS WITH ARGON

RAN PANG, DE-YIN WUa, ZHONG-QUN TIAN, College of Chemistry and Chemical Engineering, Xiamen RICHARD DAWES,ERNESTOQUINTASSANCHEZ,´ Department of Chemistry, Missouri University of Sci- University, Xiamen, China. ence and Technology, Rolla, MO, USA; KELVIN LEE, Radio and Geoastronomy Division, Harvard-Smithsonian Center for Astrophysics, Cambridge, MA, USA; MICHAEL C McCARTHY, Atomic and Molecular Physics, Water plays a very important role in surface science of electrochemical interfaces, closely associated with energy source, Harvard-Smithsonian Center for Astrophysics, Cambridge, MA, USA. environment, our living, and life processes. However, it is very difficult to be observed from normal Raman spectra of water in electrochemical interfaces. Although the surface-enhanced Raman scattering effect can have million-fold Raman Using a series of vibrationally effective PESs constructed using the automated AUTOSURF code,ab rovibrational levels signal enhancement for molecules on adsorbed silver and gold electrodes of nanostructures, the surface-enhanced Raman and predicted microwave transition frequencies of the SiS–Ar and CS–Ar complexes were computed variationally. A series spectrum of water is hard to be measured due to its very small Raman scattering cross section, weak adsorption ability, of shifting rotational transition frequencies were computed as a function of the diatom vibrational quantum number. For each and very few surface molecular number relative to the bulk. Thus only electrochemical SERS spectra of water have been system, the predicted spectra are compared with experimental microwave measurements. observed in electrode/electrolyte interfaces so far. Our present work focuses on the chemical enhancement from hydrogen a E. Quintas-Sanchez´ and R. Dawes, AUTOSURF: A Freely Available Program to Construct Potential Energy Surfaces, J. Chem. Inf. Model. 59, 262–271 (2019). bonding interaction, surface adsorption, halide ions, interfacial electric field effects on SERS signals of water adsorbed on b R. Dawes and E. Quintas-Sanchez,´ The Construction of Ab Initio-Based Potential Energy Surfaces, Reviews in Computational Chemistry, Volume 31, Chapter 5, pp. 199–263, silver electrodes, by combining the metallic cluster model and hybrid density functional theory (DFT-B3LYP) methods. The John Wiley & Sons (2018). interfacial structures, binding interactions and the anion effect from different halides including chloride, bromide, and iodide ions have been analyzed and compared with experimental measurements in literatures. Then the excited states of halide ions modified active sites on roughened silver electrode have been discussed. Especially, our time-dependent DFT (TD- DFT) calculations predicted that halide ions can form low-lying excited states of surface complexes, like the photon-induced TH08 4:45 – 5:00 electron transfer states, and finally contribute to the chemical enhancement of SERS signals of water. Furthermore, we IR-IR PREDISSOCIATION SPECTROSCOPY OF PROTONATED TRIALANINE: BEGINNING TO DETERMINE HOW proposed that the halide effect on the relative SERS intensities of water is a good example for understanding the chemical SIDE CHAINS AFFECT STRUCTURE AND SOLVATION enhancement of SERS active sites modified by halide ions in electrochemical systems. SUMMER LEE SHERMAN, KAITLYN C FISCHER, JONATHAN VOSS, ETIENNE GARAND, Department a*Email: [email protected] of Chemistry, University of Wisconsin–Madison, Madison, WI, USA.

Proteins and peptides are of interest to many different research groups across all fields of chemistry and biology. Of special interest is understanding conformational changes within proteins that occur due to different amino acid substituents, especially those that differ by just a side chain. However, it is very difficult to completely analyze a protein’s full local environment due to spectral congestion from the different conformers of each protein. Thus, small peptides (N-chain, N=1-5) are used as model systems for both floppy and non-floppy chain systems to probe the effect of the R-group on the conformation + TH06 4:09 – 4:24 population. Prior in the Garand group, conformations of protonated triglycine (Gly3H ) have been found for the bare peptide THE AUTOMATED CONSTRUCTION OF POTENTIAL ENERGY SURFACES SUITABLE TO DESCRIBE VDW COM- as well as when the peptide has one water molecule clustered around it. Therefore, in order to investigate how varying the + PLEXES OF HIGHLY EXCITED NASCENT REACTION PRODUCT MOLECULES side chain affects the conformations of these chained peptides, protonated trialanine (Ala3H ) is used due to the fact that the side chain here is changed from a hydrogen to a methyl group. Utilizing Cryogenic Ion Vibrational Spectroscopy (CIVS) and ERNESTO QUINTAS SANCHEZ´ , RICHARD DAWES, Department of Chemistry, Missouri University of Sci- electronic structure calculations, highly resolved structural features of these systems will be elucidated. Conformer-specific ence and Technology, Rolla, MO, USA; KELVIN LEE, Radio and Geoastronomy Division, Harvard-Smithsonian IR-IR double resonance techniques will be used in to quantify the contribution of various conformers. This technique will Center for Astrophysics, Cambridge, MA, USA; MICHAEL C McCARTHY, Atomic and Molecular Physics, allow the probing of how non-covalent interactions, with particular focus on intramolecular peptide H-bonding, change as Harvard-Smithsonian Center for Astrophysics, Cambridge, MA, USA. a function of side chain. From these model systems, it will then be possible to extrapolate such characterization to larger peptides. Further on, through the use of microsolvation, it will be possible to determine the changes in conformation as a Some reactions producing extremely hot nascent products—with vibrational quantum numbers at least as high as 30— function of not only the side chain, but also through water-peptide H-bonding interactions. nevertheless form relatively long-lived weakly-bound van der Waals (vdW) complexes with bath gas molecules that are ob- servable via microwave rotational spectroscopy. One example is SiO, formed in the reaction of various silanes with oxygen.a The reason for the long lifetimes of the complexes, despite having internal energies that greatly exceed the vdW well depth, is the very weak coupling between the intra- and intermolecular modes. Theoretical calculations of such unbound resonance TH09 5:03 – 5:18 states can be much more challenging than ordinary bound state calculations since approaches to deal with the dissociating COORDINATION AND STRUCTURE OF LATE TRANSITION METAL CATION (Co, Rh, Pt) ACETYLENE COM- wavefunction (such as complex absorbing potentials) are less straightforward and much more time consuming. We have PLEXES STUDIED WITH INFRARED PHOTODISSOCIATION SPECTROSCOPY demonstrated that a simplified approach of making a series of vibrationally effective PESs for the intermolecular coordinates (one for each reaction product vibrational quantum number of interest) can produce vdW levels for the complex that are of JOSHUA H MARKS, TIMOTHY B WARD, MICHAEL A DUNCAN, Department of Chemistry, University of spectroscopic accuracy. Here we will describe how our freely available PES fitting code called AUTOSURFbc can be used to Georgia, Athens, GA, USA. construct the necessary PESs using automation. The code is demonstrated here by presenting spectroscopic-quality potential energy surfaces for Ar–CS and Ar–SiS complexes. Late transition metals are studied as model systems for single atom catalysis in the gas phase with infrared photodisso- ciation spectroscopy. Clusters of M+(acetylene) (n = 1-8) are produced via laser vaporization of either cobalt, rhodium, or a n M. C. McCarthy, S. A. Ndengue´ and R. Dawes, The rotational spectrum and potential energy surface of the Ar–SiO complex, J. Chem. Phys. 149, 134308 (2018). platinum rods in a supersonic expansion of argon containing acetylene. Infrared photodissociation spectroscopy of smaller b E. Quintas-Sanchez´ and R. Dawes, AUTOSURF: A Freely Available Program to Construct Potential Energy Surfaces, J. Chem. Inf. Model. 59, 262–271 (2019). c R. Dawes and E. Quintas-Sanchez,´ The Construction of Ab Initio-Based Potential Energy Surfaces, Reviews in Computational Chemistry, Volume 31, Chapter 5, pp. 199-263, clusters is accomplished with the aid of argon tagging. Larger clusters are studied through the elimination of one or more John Wiley & Sons (2018). acetylene ligands. These spectra are assigned with the aid of B3LYP/Def2TZVP computations. The structure and size of the inner coordination sphere is discussed. 112 113 TI. Small molecules TH10 5:21 – 5:36 Tuesday, June 18, 2019 – 1:45 PM TRANSFERRING POLARIZABILITIES FROM DIATOMICS TO LARGER MOLECULES Room: 1024 Chemistry Annex STEPHEN L COY, TIMOTHY J BARNUM, ROBERT W FIELD, Department of Chemistry, MIT, Cambridge, MA, USA; BRYAN M. WONG, Department of Chemistry, University of California, Riverside, Riverside, CA, Chair: Dennis W. Tokaryk, University of New Brunswick, Fredericton, NB, Canada USA.

Because of the involvement of low-lying 3d levels in bonding and polarizability, calcium resembles an early transition metal. In a biological context, calcium has bonding flexibility, high availability, and is an essential component of many proteins. It is metered or gated by voltage or ligands through calcium channels, and is processed and remodeled in bone and shell structure. TI01 1:45 – 2:00 In the case of diatomics, ab-initio calculations and the interpretation of Rydberg spectra can be used to infer effective JON HOUGEN’S MONOGRAPH NBS 115 atomic charges, and dipole-dipole or dipole-quadrupole polarizability for the Ca cation, and charge and dipole-dipole polar- izability for the ligand. Calculations with an external point-charge perturbation can provide additional types of molecular ROBERT W FIELD, Department of Chemistry, MIT, Cambridge, MA, USA. polarizability values. Calculations on calcium difluoride, CaF2, which, surprisingly, is non-linear, can provide the same type of information I was a graduate student in the Klemperer group in 1970 when Jon Hougen’s ”The Calculation of Rotational Energy about the atomic constituents. We compare the metal and ligand effective atomic electric properties of the diatomic and Levels and Rotational Line Intensities in Diatomic Molecules” appeared. Physical Chemists like to break stuff. My favorite triatomic, and compare to the values used for biological systems. topic, spectroscopic perturbations, presents a rich variety of broken patterns. I began as a collector and NBS 115 both gave me tools to add to my collection and a challenge to look beyond molecular constants. My perturbations were more than molecules behaving badly. The 49 pages of NBS 115 became the foundation of my career as a spectroscopist. Jon Hougen wrote defining guides for many areas of spectroscopy, thereby providing the foundations for many careers. Each such guide echoed the elegant simplicity of NBS 115.

TI02 2:03 – 2:18 1 DIRECT POTENTIAL FIT FOR THE X Σ STATE OF F2: PERTURBATION OF THE HIGHEST OBSERVED V=22 VIBRATIONAL LEVEL

ROBERT W FIELD, Department of Chemistry, MIT, Cambridge, MA, USA; JOHN COXON, Department of Chemistry, Dalhousie University, Halifax, NS, Canada; PHOTOS HAJIGEORGIOU, Centre for Primary Care and Population Health, School of Medicine, University of Nicosia, Nicosia, Cyprus.

The high-resolution vacuum-uv spectrographic data1 for the C - X emission and C,(D,E),H,h,I - X(v = 0) absorption 2 3 transitions of F2, in combination with pure rotation and vibration-rotation Raman data, have been employed in a least- squares analysis. Attention was given to the extensive blending in the absorption data and to account for plate-to-plate shifts in the emission data. The C - X data, with an estimated uncertainty of 0.05 cm−1, sample X state vibrational levels v = 1 - 22,for which the potential energy function was fitted using the extended-MLR model4. 3549 line positions in the weighted fit provided estimates of 1303 term values of excited electronic states and 17 parameters for the ground state. The highest cm−1 2 2 observed v = 22 level of the ground state, which lies only 114 below the F( P3/2)+F( P3/2) dissociation limit, is found to be perturbed; all rotational levels (J = 0 - 19) lie at energies 5 - 13 cm−1below their expected positions. A deperturbation model was employed within the direct potential fit; in this novel approach, the eigenvalue of each J-level in v = 22 was determinedfroma2x2matrix,withthediagonal level of the perturbing state represented by Ep +BpJ(J+1), and the off- diagonal element by a + b(J + 1/2). However, the b-parameter was indeterminate; a successful fit of the entire data set with −1 −1 inclusion of the deperturbation model for v = 22 provided the estimates Ep = -70.5(3.7) cm ,Bp = 0.226(6) cm ,a= −1 16.2(8) cm and Re = 1.412555(4)A.˚ There is much interest in an identification of the perturbing state. The results indicate −1 a J-independent spin-orbit interaction with a weakly-bound perturbing state (Re =2.8A),˚ lying 40 - 50 cm above v = 22. + The absence of a J-dependent b(J + 1/2) Coriolis interaction implies a perturber with 0g symmetry. A plausible candidate is + the a’(0g ) state which dissociates to the same atomic limit and which is repulsive at short-R. 1. E.A. Colbourn, M. Dagenais, A.E. Douglas, J.W. Raymonda, Can. J. Phys. 54 (13) (1976) 1343-1359. 2. H.G.M. Edwards, E.A.M. Good, D.A. Long, J. Chem. Soc. Faraday Trans. 272 (1976) 984-987. 3. R.Z. Martinez, D. Bermejo, J. Santos, P. Cancio, J. Mol. Spectrosc. 168 (1994) 343-349. 4. R.J. Le Roy, N.S. Dattani, J.A. Coxon, A.J. Ross, P. Crozet, C. Linton, J. Chem. Phys. 131 (2009) 204309. 114 115

TI03 2:21 – 2:36 TI05 2:57 – 3:12 3 FINE AND HYPERFINE ANALYSIS OF RUTHENIUM MONOBORIDE ISOTOPOLOGUES. HYPERFINE STRUCTURE IN THE (2-0) [18.3]3-X Δ3 TRANSITION OF COBALT MONOBORIDE.

JACOB M DORE, ALLAN G. ADAM, Department of Chemistry, University of New Brunswick, Fredericton, JACOB M DORE, ALLAN G. ADAM, Department of Chemistry, University of New Brunswick, Fredericton, NB, NB, Canada; COLAN LINTON, DENNIS W. TOKARYK, Department of Physics, University of New Brunswick, Canada; COLAN LINTON, DENNIS W. TOKARYK, Department of Physics, University of New Brunswick, Fredericton, NB, Canada. Fredericton, NB, Canada.

Using diborane, B2H6, as a reactant gas and ruthenium as the target metal in the UNB laser ablation molecular jet ap- Cobalt monoboride molecules were produced in the UNB laser ablation molecular jet apparatus using diborane, B2H6, 3 paratus, ruthenium monoboride molecules have been detected using laser-induced fluorescence spectroscopy. The [18.4]2.5- as the reactant gas and cobalt as the target metal. Fine and hyperfine interaction parameters in the [18.3]3 (v’=2) and X Δ3 2Δ a X 5/2 electronic transition of RuB has been observed previously at pulsed-dye laser resolution . Three vibronic bands were (v”=0) states of CoB have been determined from an analysis of the high-resolution laser-induced fluorescence (LIF) spectrum 11 10 3 rotationally analyzed and designated as the (1-0), (0-0) and (0-1) bands, but only the Ru B and Ru B isotopologues were of the (2, 0) [18.3]3-X Δ3 electronic transition. This transition along with three others have been studied previously at resolved. Ruthenium has 7 naturally occurring isotopes ranging from 1.87% to 31.55% abundance, giving a total combination pulsed-dye laser resolution by Ng et al.a Herein we report updated rotational parameters for CoB, as well as hyperfine 59 of 14 isotopologues for RuB. Using our cw-ring dye laser, the three vibronic bands were recorded at high resolution and 12 interaction parameters arising from the strong nuclear interaction of Co (I=7/2, μ/μN =4.627). CoB has two naturally of the isotopologues have been rotationally analyzed. Both of the odd isotopes of Ru have a nuclear spin I=5/2 and their occurring isotopologues, Co11BandCo10B, but the 10B isotopologue (19.0% abundance) was not analyzed due to a much respective isotopologues had resolved hyperfine structure which was analyzed to extract the hyperfine parameters. It was weaker LIF signal. A hyperfine comparison between CoB and IrB is presented. Both CoB and IrB are group 9 transition 101 99 determined that the hyperfine interaction arises from the nuclear spin of the Ru and Ru atoms and not from the boron metal monoborides that share a valence electronic configuration of δ3σ in their ground states. nucleus. aNg, Y. W., Pang, H. F. and Cheung, A. S. C. J. Chem. Phys. 135, 1–6 (2011). aWang, N., Ng, Y. W. and Cheung, A. S. Chem. Phys. Lett. 547, 21-23 (2012).

Intermission

TI06 3:51 – 4:06 FIRST IDENTIFICATION OF A 2Δ STATE OF CaH IN THE VISIBLE REGION.

JIN FURUTA, KYOHEI WATANABE, IORI TANI, KAORI KOBAYASHI, YOSHIKI MORIWAKI, Department TI04 2:39 – 2:54 of Physics, University of Toyama, Toyama, Japan; STEPHEN CARY ROSS, Department of Physics, University of New Brunswick, Fredericton, NB, Canada. ISOTOPE INVARIANT FITTING OF GeO AND GeS AND THE 73Ge QUADRUPOLE MOMENT DERIVED FROM SPECTROSCOPY AND QUANTUM CHEMICAL CALCULATIONS Calcium monohydride CaH is a simple diatomic molecule found in the Sun and other stars. The A-X electronic spectrum of CaH has been a useful probe for classifying stars. This has lead to nearly a century of spectroscopic work on CaH, with SVEN THORWIRTH, I. Physikalisches Institut, Universitat¨ zu Koln,¨ Koln,¨ Germany; KELVIN LEE, Radio 2 + 2 + the first laboratory spectrum being the C Σ -X Σ transition in the near-UV region reported by Mulliken.a and Geoastronomy Division, Harvard-Smithsonian Center for Astrophysics, Cambridge, MA, USA;MARIE- We have recently been working on this molecule in the visible and ultraviolet regions and have identified many new vibra- ALINE MARTIN-DRUMEL, Institut des Sciences Moleculaires´ d’Orsay, Universite´ Paris-Sud, Orsay, France; tional levels of the B/B state using Laser Induced Fluorescence (LIF). Our primary interest has been the detailed investigation BRETT A. McGUIRE, NAASC, National Radio Astronomy Observatory, Charlottesville, VA, USA;FLORIAN of the B/B state which has a double-minimum potential energy function. Our previous LIF work was on vibrational levels KREUTER, FRANZISKA ENGEL, STELLA STOPKOWICZ, JURGEN¨ GAUSS, Institut fur¨ Physikalische in the energy regime lying above the potential energy barrier between the two wells.b, c We were able to confirm the strong Chemie, Universitat¨ Mainz, Mainz, Germany; CRISTINA PUZZARINI, Dep. Chemistry ’Giacomo Ciamician’, irregularity in the vibrational energy spacings that had been predicted by the quantum chemical study of Carlsund-Levin et University of Bologna, Bologna, Italy; STEPHAN SCHLEMMER, I. Physikalisches Institut, Universitat¨ zu Koln,¨ al.d This irregularity is due to interaction between the vibrational levels of the B/B and D states. Koln,¨ Germany; MICHAEL C McCARTHY, Atomic and Molecular Physics, Harvard-Smithsonian Center for We have also investigated the energy regime which starts from just below the minimum of the higher lying outer potential Astrophysics, Cambridge, MA, USA. well and continues to just above the potential energy barrier between the two wells. There we identified the A-X(4, 0) and −1 Diatomic germanium oxide, GeO, and germanium sulfide, GeS, have been studied by Fourier transform microwave B/B -X(3 or 5, 0) bands and also new vibronic levels around 18,400-20,000 cm which do not belong to any of the A, B, or E states. We conclude that these new levels belong to the previously unobserved lowest lying 2Δ state. spectroscopy using laser ablation from a germanium target rod in the presence of H2SorO2 diluted in neon. Extensive isotopic spectroscopy has been performed; measurements include the ground vibrational state as well as states exceeding We are investigating evidence for possible interactions with other electronic states. We also outline the current status of our work and future prospects as we continue our program of delineating the vibrational levels of the B state over their full v =10for some species. Ground state rotational spectra of several GeS isotopologs have also been studied around 300 GHz energy range: starting at the energy of the minimum of the inner well, progressing through the energy of the minimum of the through a DC discharge of GeCl4 and H2S in a free-space absorption cell. A global isotope invariant fit has been performed combining all previously published and new high-resolution spectroscopic data. From the analysis of the 73Ge data combined outer well, the energy of the barrier, and on towards the dissociation limit. 73 with highly accurate quantum chemical values for the germanium electric-field gradient, a revised Ge quadrupole moment aR. S. Mulliken, Phys. Rev. 25, 509 (1925). has been derived. bK. Watanabe, N. Yoneyama, K. Uchida, K. Kobayashi, F. Matsushima, Y. Moriwaki, S. C. Ross, Chem. Phys. Lett. 657, 1 (2016). cK. Watanabe, I. Tani, K. Kobayashi, Y. Moriwaki, S. C. Ross, Chem. Phys. Lett. 710, 11 (2018). dC. Carlsund-Levin, N. Elander, A. Nunez, A. Scrinzi, Phys. Scripta 65, 306 (2002). 116 117

TI07 4:09 – 4:24 TI10 5:03 – 5:18 MICROWAVE SPECTROSCOPY OF OXAZOLE AND ISOXAZOLE THEORY OF NEAR-RESONANT INTRACAVITY ENHANCED TWO-PHOTON ABSORPTION

KAORI KOBAYASHI, SHOZO TSUNEKAWA, Department of Physics, University of Toyama, Toyama, Japan. KEVIN LEHMANN, Departments of Chemistry and Physics, University of Virginia, Charlottesville, VA, USA.

Oxazole and isoxazole (C3H3NO) are isomers of five membered ring molecules with two hetero-atoms, nitrogen and All polyatomic molecules have IR allowed fundamentals, 0 → νs, each of which has a corresponding “hot band” oxygen. Some amino acids contains five membered ring structure. Previous microwave spectroscopic studies were carried νs → 2νs that has an origin shifted by 2Xss from the corresponding fundamental, where Xss is the diagonal anharmonic out in the low frequency region abcdefand it is desirable to have information for future interstellar detection. In this study, spectroscopic constant for mode s. There will always be Doppler-free two-photon absorption transitions where a P (J) tran- pure rotational spectroscopy was carried out by using conventional microwave spectroscopy and chirp-pulse Fourier-transform sition of the fundamental will be nearly resonant with a R(J − 1) transition of the hot band. For bands with Q branches, spectroscopy with a waveguide cell. Up to 340 GHz was observed at room temperature. Previous molecular constants made there is also the possibility for near-resonant Q followed by R transitions and for P followed by Q branch transitions. For assignment straightforward and detailed analysis using Watson’s Hamiltonian will be reported. a linear molecule without missing levels, the maximum detuning from exact 2-photon resonance will be less than B,the rotational constant of the molecule. For symmetric and asymmetric tops, the multiple branches increase the probability of a aW. C. Mackrodt, A. Wardley, P. A. Curnuck, N. L. Owen, J. Sheridan, Chem. Commun. (London), 692 (1966). bO.L. Stievater, P. Nosberger¨ and J. Sheridan, Chem. Phys. Lett. 710, 11 (2018). very near resonance. I have derived general expressions for the two-photon absorption cross section for such transitions and cO. L. Stiefvater, J. Chem. Phys. 63, 2560 (1975). have assembled predictions for cases where the necessary data is available in HITRAN. dA. Kumar, J. Sheridan, O. L. Stiefvater, Z. Naturforsch. 33a, 145 (1978). The resonant enhancement combined with the intracavity intensity enhancement leads to cases of strong and selective eA. Kumar, J. Sheridan, O. L. Stiefvater, Z. Naturforsch. 33a, 549 (1978). fU. Spoerel, H. Dreizler, and W. Stahl, E. Kraka, D. Cremer, J. Phys. Chem. 100, 14298 (1996). two-photon absorption, particularly at low pressure, in some cases even stronger than one-photon absorption as the entire population of the lower state can be pumped rather than only molecules with Doppler shifts within a power-broadened ho- mogeneous width. The one and two-photon absorption contributions to the cavity decay can be separately fit, uncoupling the TI08 4:27 – 4:42 two-photon absorption from other sources of cavity lass. I previously published, App. Phys B 116, 147 (2014), an analysis of PURE-ROTATIONAL RAMAN AND ELECTRONIC-RAMAN SPECTRUM OF NITRIC OXIDE the expected sensitivity limit of such a combined fit in both the detector noise and shot noise limited cases. Combined with the approximately two orders of magnitude increase in resolution, and the fact that the two-photon absorption spectrum will AMAN SATIJA, ROBERT P. LUCHT, Mechanical Engineering, Purdue University, West Lafayette, IN, USA. be extremely sparse due to the near-resonance requirement, this should provide extremely high sensitivity and unprecedented selectivity for trace detection in low-pressure gases. Nitric Oxide (NO) is a combustion pollutant known for its role in the for- An experimental apparatus is currently being assembled to experimentally verify these predictions and it is hoped that mation of photochemical smog. Nitric oxide is also interesting from the view- preliminary data will be available at the time of the meeting. point of fundamental spectroscopy since it has two closely spaced ground elec-

Data

1.0

Theory tronic states. Consequently, in addition to pure-rotational Raman spectrum, NO 1.0 −1 also exhibits electronic-Raman spectrum near 120 cm . We applied a dual- 0.8

0.8

pump combined CARS system (DPCCS) to investigate the spectrum of NO. In 0.6 a DPCCS, in contrast to a typical pure-rotational CARS system, all beams have 0.6

0.4 different wavelengths. This allows us to preferentially suppress Q or S branch 0.4 Calculated Spectrum Calculated

0.2

Raman transitions and investigate the polarization character of a target molecule, Sqrt. Intensity (arb. units)

0.2 in this case NO. Theoretical spectrum of NO was calculated by solving the time- 0.0

0.0 dependent Schrodinger wave equation using perturbation theory. By comparing 25 50 75 100 125 150 175 200

-1 the measured and the computed spectrum we obtain the anisotropy of the po- Wavenumber /cm larizability tensor of NO as well as a quantitative estimate of the strength of electronic-Raman transitions. The figure in this abstract shows comparison between CARS data and calculated NO spectrum Π with no preferential suppression of either the Q or S branch Raman transitions. Notice the spin-splitting of the 2 1/2 and 2 Π −1 3/2 states of NO, evident, near a Raman shift of 80 cm .

TI09 4:45 – 5:00 HIGH-TEMPERATURE METHANE ABSORPTION WITH A DUAL FREQUENCY COMB SPECTROMETER

NATHAN A MALARICH, DAVID YUN, Mechanical Engineering, University of Colorado at Boulder, Boulder, CO, USA; SEAN COBURN, Department of Mechanical Engineering, University of Colorado Boulder, Boulder, CO, USA; KEEYOON SUNG, BRIAN DROUIN, Jet Propulsion Laboratory, California Institute of Technology, Pasadena, CA, USA; GREGORY B RIEKER, Department of Mechanical Engineering, University of Colorado Boulder, Boulder, CO, USA.

Quantitative measurements of combustion system fueling and hot-Jupiter exoplanets require accurate methane absorption data at elevated temperatures. The ExoMol and HITRAN spectral databases in the near-infrared 6500-9000cm-1 range are based on the 10to10 potential energy surface, and the 80K and 296K empirical WKLMC linelist, respectively, which do not empirically constrain all elevated-temperature behavior. We present spectra of the near-infrared methane overtone band around 1400nm at temperatures from 296 K to 900 K. The spectra are taken using a three-zone tube furnace and a dual- frequency comb spectrometer with 600 cm-1 bandwidth and .00667cm-1 resolution. These measurements are targeted toward providing a compact, accurate methane absorption linelist for 300-900K. 118 119

TJ. Conformers and isomers TJ02 2:03 – 2:18 A STUDY OF THE CONFORMATIONAL ISOMERISM OF N-PROPYL NITRATE BY MICROWAVE SPECTROSCOPY Tuesday, June 18, 2019 – 1:45 PM W. ORELLANA, SUSANNA L. STEPHENS, STEWART E. NOVICK, Department of Chemistry, Wesleyan Uni- versity, Middletown, CT, USA; S. A. COOKE, Natural and Social Science, Purchase College SUNY, Purchase, Room: 217 Noyes Laboratory NY, USA; CAROLYN BRAUER, THOMAS A. BLAKE, Chemical Physics, Pacific Northwest National Labora- tory, Richland, WA, USA.

The rotational spectrum of n-propyl nitrate was measured in the frequency range between 6-18 GHz using a Balle-Flygare Chair: Jennifer van Wijngaarden, University of Manitoba, Winnipeg, MB, Canada 13 15 Fourier transform microwave jet/cavity spectrometer. Parent, C and N isotopologue transitions for the lower-energy anti- gauche (AG) conformer were found using this instrument. The search for spectra from other conformers was performed using a broadband chirped-pulse jet spectrometer. Transitions from the anti-anti (AA) conformer were observed in this manner. Parent, 13Cand15N isotopologue transitions for the AA conformer were rescanned using the cavity instrument to improve resolution and the signal-to-noise ratio. Rotational, centrifugal distortion, and nuclear electric quadrupole coupling constants for all conformers/isotopologues were fit using Pickett’s SPFIT program. The structure of n-propyl nitrate will be discussed in light of these results.

TJ01 1:45 – 2:00 HIGH RESOLUTION FAR-INFRARED SPECTROSCOPY OF TRANS- AND GAUCHE-BUTADIENE Anti-Anti Anti-Gauche

MARIE-ALINE MARTIN-DRUMEL, CNRS, Institut des Sciences Moleculaires d’Orsay, Orsay, France; JESSIE P PORTERFIELD, Atomic and Molecular Physics, Harvard Smithsonian Center for Astrophysics, Cam- bridge, MA, USA; JOSHUA H BARABAN, Chemistry, Ben-Gurion University of the Negev, Beer-Sheva, Israel; BRYAN CHANGALA, JILA, National Institute of Standards and Technology and Univ. of Colorado Department TJ03 2:21 – 2:36 of Physics, University of Colorado, Boulder, CO, USA; MATTHEW NAVA, Department of Chemistry and Chem- CONFORMATIONAL ISOMERISM OF N-BUTYL NITRATE STUDIED BY MICROWAVE SPECTROSCOPY ical Biology, Harvard University, Cambridge, MA, USA; MANUEL GOUBET, Laboratoire PhLAM, UMR 8523 CNRS - Universite´ Lille 1, Villeneuve d’Ascq, France; PIERRE ASSELIN, CNRS, De la Molecule´ aux Nano- SUSANNA L. STEPHENS, Department of Chemistry, Wesleyan University, Middletown, CT, USA;JOSHUA Objets: Reactivit´ e,´ Interactions, Spectroscopies, MONARIS, Sorbonne Universite´ , PARIS, France;PASCALE A. SIGNORE, Chemistry , Wesleyan University , Middletown, CT, USA; CAROLYN BRAUER, THOMAS A. SOULARD, MONARIS UMR8233, CNRS - UNiversite´ Paris 6 UPMC, Paris, France; ROBERT GEORGES, BLAKE, Chemical Physics, Pacific Northwest National Laboratory, Richland, WA, USA; S. A. COOKE, Natu- IPR UMR6251, CNRS - Universite´ Rennes 1, Rennes, France; OLIVIER PIRALI, AILES beamline, Synchrotron ral and Social Science, Purchase College SUNY, Purchase, NY, USA; STEWART E. NOVICK, Department of SOLEIL, Saint Aubin, France; BRANT E. BILLINGHURST, EFD, Canadian Light Source Inc., Saskatoon, Chemistry, Wesleyan University, Middletown, CT, USA. Saskatchewan, Canada; JOHN F. STANTON, Physical Chemistry, University of Florida, Gainesville, FL, USA; MICHAEL C McCARTHY, Atomic and Molecular Physics, Harvard-Smithsonian Center for Astrophysics, Cam- The rotational spectrum of n-butyl nitrate was measured with a chirped pulse Fourier transform microwave spectrometer bridge, MA, USA. over the range of 7-13 GHz. This allowed for the identification and assignment of five conformers, AGA, GAA, GGA, AAA, and GG’A with intensity ratios of approximately 1 : 0.2 : 0.2 : 0.1 : 0.1. These conformers were subsequently investigated by Much attention has surrounded 1,3-butadiene because this conjugated diene, the simplest of all, is an ideal candidate to Balle-Flygare Fourier transform microwave spectroscopy in order to resolve the nuclear electric quadruople coupling splitting observe the effects of π-electron delocalization, and because the species is of central importance in a wide range of chemistry and for further transitions to be collected, allowing improved fitting. Isotopic substitutions at natural abundance were also applications. Butadiene exists in two forms, the most stable planar trans and the long-elusive gauche lying 12 kJ/mol higher observed for the AGA conformer. Quantum chemical calculations reveal that the AGA conformer is the lowest in energy. in energy. The later was only conclusively detected in the gas phase by some of us recently, in a work that allowed the A variety of computational methods were used to explore the energy ordering and barriers between inter-conversion of the determination of a partial structure from a combination of pure rotational measurements and high level quantum chemical lowest lying energy conformers. This work extends a series of other alkyl nitrate works studied by microwave and mm-wave calculations. spectroscopy.abc In an attempt to detect the ro-vibrational spectrum of gauche-butadiene, we have re-investigated the far-infrared spectrum      of the species at both the SOLEIL synchrotron facility and the Canadian light source using three experimental set-ups allowing to reach rotational temperatures ranging from 30 to 350 K. We will present our results on new fundamentals of the trans form, and on the gauche form.

aMethyl Nitrate; W.B. Dixon, E.B. Wilson, J. Chem. Phys., 35, 191 (1961) bEthyl Nitrate; D.G. Scroggrin, J.M. River, E.B. Wilson, J. Chem. Phys., 60, 1376 (1974); J. Thomas, I. Medvedev, D. Dolson, ISMS 2014 cn-Propyl Nitrate; W. Orellana, S.L. Stephens, S.E. Novick, S.A. Cooke, C. Brauer, T.A. Blake, ISMS 2019 120 121

TJ04 2:39 – 2:54 TJ07 4:09 – 4:24 1-IODOPENTANE, EXPERIMENTS AND CALCULATIONS THE CONFORMATIONAL PANORAMA OF MANDELIC ACID

SUSANNA L. STEPHENS, JOSHUA A. SIGNORE, Department of Chemistry, Wesleyan University, Middle- LUCIE KOLESNIKOVA´ , ELENA R. ALONSO, SANTIAGO MATA, JOSEL.ALONSO,´ Grupo de Espectro- town, CT, USA; LAN CHENG, Department of Chemistry, Johns Hopkins University, Baltimore, MD, USA; scopia Molecular, Lab. de Espectroscopia y Bioespectroscopia, Unidad Asociada CSIC, Universidad de Val- WILLIAM C. BAILEY, Department of Chemistry-Physics, Kean University (Retired), Union, NJ, USA;S.A. ladolid, Valladolid, Spain. COOKE, Natural and Social Science, Purchase College SUNY, Purchase, NY, USA;STEWARTE.NOVICK, Department of Chemistry, Wesleyan University, Middletown, CT, USA. The conformational landscape of mandelic acid (phenyl glycolic acid), the simplest alpha-hydroxy acid containing an aromatic substituent, has been unveiled by laser ablation coupled with broadband Fourier transform microwave spectroscopy The rotational spectra of two conformers, GAA and AAA, of 1-iodopentane have been recorded using both Fourier LA-CP-FTMW. The four identified conformers provide the first global structural picture of this molecule traditionally used transform microwave cavity and chirp spectrometers. Iodine has a large nuclear electric quadrupole coupling tensor, χ,andis in cosmetics and dermatology as well as in the synthesis of pharmaceuticals. Rotational transitions of singly substituted 13C heavy enough to require a relativistic calculation for ab initio field gradient calculations. We will present a comparison of the isotopic species of the most stable conformer in its natural abundances were also detected, providing insight on its geometry. experimental results, a calculation involving a clever scaling of the χ tensor,a and a direct relativistic ab initio calculation.b

aW.C. Bailey and F.M. Gonzalez J. Mol. Spectro., 651-653, 689-695 (2003) bL. Cheng, J. Gauss, J. Chem. Phys., 134, 244112 (2011)

Intermission

TJ05 3:33 – 3:48 DISPERSION-DRIVEN ISOMERISM IN THE GAS PHASE: THEORETICAL AND MICROWAVE SPECTROSCOPIC STUDY OF ALLYL ISOCYANATE

WENHAO SUN, OLAMIDE P. SOGEKE, WESLLEY G. D. P. SILVA, JENNIFER VAN WIJNGAARDEN, Department of Chemistry, University of Manitoba, Winnipeg, MB, Canada. TJ08 4:27 – 4:42 CH =CHCH NCO The pure rotational spectrum of allyl isocyanate ( 2 2 ) was studied using chirped pulse and Balle- 4 Flygare Fourier Transform microwave (FTMW) spectroscopy. Besides the previously reported gauche conformer,a the lowest CONFORMATION SPECIFIC SPECTROSCOPY OF AC-γ -PHE-NHME: RELATIVE ABUNDANCES IN A SUPER- energy conformer was identified for the first time with the assistance of the quantum-chemical calculations performed at SONIC EXPANSION DETERMINED USING IR POPULATION TRANSFER the B3LYP-D3(BJ) and MP2 levels of theory with Dunning’s cc-pVQZ basis set. The assignments were confirmed by the JOSHUA L. FISCHER, KARL N. BLODGETT, CHRISTOPHER P HARRILAL, TIMOTHY S. ZWIER, De- resolved hyperfine structure due to the 14N quadrupole moment and the spectra of the corresponding 13C, 15Nand18O singly partment of Chemistry, Purdue University, West Lafayette, IN, USA. substituted isotopologues in natural abundance. Rotational transitions of the most stable conformer revealed a tunneling splitting due to the interconversion motion between its two mirror images, and the tunneling path was established theoretically. Foldamers are peptides synthesized to adopt specific motifs, for instance, helices. One class of foldamers that has In addition, benchmark calculations of various density functionals with and without dispersion corrections were carried out received particular attention are β-peptides,with two carbons between amide groups, or γ-peptides, with three. This extension to investigate the effect of the short-range dispersion energy on the conformational structures. of the carbon backbone provides additional conformational flexibility and more choice for the position(s) of peptidomimetic 2 aS. Maiti, A. I. Jaman, and R. N. Nandi, J. Mol. Spectrosc. 158, 8-13 (1993) substitution. Previous gas-phase jet-cooled conformation specific spectroscopy of the γ-peptide, Ac-γ -Phe-NHMe, found three different conformers and provided the first spectroscopic signature of amide stacking.[1] The study also utilized infrared population transfer (IRPT) studies that determined the relative population of each conformer in the expansion, and later, the binding of a single water molecule.[2] Here, we expand the study further to include Ac-γ4-Phe-NHMe. Repositioning of TJ06 3:51 – 4:06 the peptidomimetic side chains from the 2- to the 4-position of γ-peptides has been shown to induce helix formation in solution. This motivates a study of the intrinsic change in conformational preferences induced by γ2-vs.γ4-Phe substitution. MICROWAVE SPECTROSCOPIC AND THEORETICAL EXAMINATION OF ALLYL ISOTHIOCYANATE CONFOR- 4 MATIONAL SPACE Conformation specific IR-UV double resonance spectra were recorded for the jet-cooled γ conformers in the NH stretch and amide I/II regions. DFT calculations at the B3LYP level of theory (6-31+G(D), D3BJ) were compared with experiment JOSEPH STITSKY , WENHAO SUN, WESLLEY G. D. P. SILVA, JENNIFER VAN WIJNGAARDEN, De- to assign structures. Two structures were assigned as phenyl rotamers of a nine-membered ring closed by an NH. . . O=C partment of Chemistry, University of Manitoba, Winnipeg, MB, Canada. hydrogen bond (C9). Tentative assignment for the third conformer is to a strained seven-membered ring closed by a hydrogen bond. Currently, IRPT is being used to determine the relative populations of the conformers in the expansion. Additionally, 4 A spectroscopic analysis of allyl isothiocyanate (CH2 =CHCH2NCS) was conducted via chirped-pulse and Balle- Ac-γ -Phe-NHMe•H2O will be studied to compare bare and partially solvated structures. Flygare Fourier Transform microwave (FTMW) spectroscopy in the 7-25 GHz range. Rotational transitions associated with [1] James III, W. H.; Muller,¨ C. W.; Buchanan, E. G.; Nix, M. G.; Guo, L.; Roskop, L.; Gordon, M. S.; Slipchenko, L. V.; the different conformers were assigned based on information gathered from quantum-chemical calculations computed at Gellman, S. H.; Zwier, T. S., J. Am. Chem. Soc. 2009, 131, 14243-14245. [2] Buchanan, E. G.; James III, W. H.; Gutberlet, B3LYP-D3(BJ) and MP2 levels of theory using the Dunning cc-pVTZ basis set. The results showed the existence of two A.; Dean, J. C.; Guo, L.; Gellman, S. H.; Zwier, T. S., Faraday Discuss. 2011, 150, 209-226. conformers, the gauche conformer, which was reported in previous worka as well as the first reported existence of a second conformer which corresponds to the global minimum. Spectroscopic assignments included transitions due to both parent conformers, 34S, 13Cand15N singly substituted isotopic species as well as hyperfine splitting due to the presence of 14N.

aMaiti, S.; Jaman, A. I.; Nandi, R. N. J. Mol. Spectrosc. 165 (1994), 168-172 122 123 TK. Mini-symposium: High-Harmonic Generation and XUV Spectroscopy TJ09 4:45 – 5:00 Tuesday, June 18, 2019 – 1:45 PM THE ROLE OF TYROSINE IN STABILIZING GAS PHASE ZWITTERIONIC CONFIGURATIONS OF PEPTIDE IONS Room: B102 Chemical and Life Sciences REVEALED BY IR-UV DOUBLE RESONANCE SPECTROSCOPY Chair: Josh Vura-Weis, University of Illinois at Urbana-Champaign, Urbana, IL, USA CHRISTOPHER P HARRILAL, Department of Chemistry, Purdue University, West Lafayette, IN, USA;AN- THONY PITTS-MCCOY, Chemistry, Purdue University, West Lafayette, IN, USA; SCOTT A McLUCKEY, TIMOTHY S. ZWIER, Department of Chemistry, Purdue University, West Lafayette, IN, USA. TK01 1:45 – 2:00 Growing experimental evidence suggests that zwitterionic structures are more prevalent in isolated gas phase environ- WELCOME AND INTRODUCTIONS ments than previously thought. These strong electrostatic interactions can govern the conformational landscape, alter frag- mentation pathways, and promote unique chemistry upon UV irradiation. It is therefore crucial to develop methods that JOSH VURA-WEIS, Department of Chemistry, University of Illinois at Urbana-Champaign, Urbana, IL, USA; specifically probe for zwitterionic interactions and provide a deeper understanding of the structural factors which promote ROBERT BAKER, Department of Chemistry and Biochemistry, The Ohio State University, Columbus, OH, USA; their stability. In this study we probe a series of arginine containing peptides cooled to 10 K using IR-UV double resonance SCOTT G SAYRES, School of Molecular Sciences, Arizona State University, Tempe, AZ, USA. spectroscopy. The main peptide sequences interrogated were YGRAR and FGRAR. Using the IR signatures of the hydride This talk will provide an introduction to this mini-symposium, which features advances in high-harmonic generation stretch as well as in the amide I/II regions it was possible to identify conformers which were zwitterionic. IR signatures and the spectroscopy it enables. This strong-field process is a sensitive probe of small-molecule electronic structure, as the reveal that YGRAR mainly adopts a zwitterionic configuration. The assigned structure for singly protonated YGRAR shows spectrum of the extreme ultraviolet (XUV) photons produced by the ionization-recollision process measures the shape and that the tyrosine OH and the middle protonated arginine residue work in tandem to solvate the carboxylate anion, while the energy of the molecular orbitals. Furthermore, the XUV pulse can be used as an element-specific probe of electron dynamics C-terminal arginine plays a seemingly minor role in stabilizing the structure. As a consequence of the tyrosine OH engaging in molecules and materials at femtosecond to attosecond timescales. in a strong hydrogen bond with a highly basic site, the electronic origin transition of the zwitterionic species is shifted by 400 cm−1to lower energy compared to non-zwitterionic structures. The magnitude of this shift is somewhat lessened by the C-terminal protonated arginine which acts as a hydrogen bond donor to the tyrosine hydroxyl oxygen. A further consequence of this hydrogen bond is the presence of an underlying broad component to the UV spectrum. It is postulated that this broad TK02 2:03 – 2:18 absorption is caused by an excited state hydrogen transfer between the tyrosine chromophore and carboxylate group. Similar UNDERSTANDING CARRIER AND ELEMENT SPECIFIC DYNAMICS IN ORGANOHALIDE PEROVSKITE BY UV induced reactions have been observed in neutral clusters of phenol and ammonia. The importance of the hydrogen bond FEMTOSECOND TABLETOP XUV SPECTROSCOPY between the carboxylate and tyrosine OH is showcased by FGRAR, which does not form a zwitterion. These results show that neutral sidechains can play a large role in promoting zwitterionic structure in addition to the presence of highly basic AASTHA SHARMA, MAX A VERKAMP, JOSH VURA-WEIS, Department of Chemistry, University of Illi- residues. nois at Urbana-Champaign, Urbana, IL, USA.

TJ10 5:03 – 5:18 Hybrid organic-inorganic halide perovskites, such as methylammonium lead iodide have emerged as outstanding light absorbing and emitting materials in recent years. Quasi-2D/layered perovskites have also gained significant attention owing JET-COOLED, CONFORMER-SPECIFIC IR SPECTRA OF CYCLICALLY-CONSTRAINED β-PEPTIDES. DOES CON- to enhanced ambient stability, high luminescence quantum yield and strong excitonic effects. However, our current under- DENSED PHASE STRUCTURE SURVIVE THE VACUUM? standing of the fundamental photophysics in these materials is limited by the overlap of spectral features in the energy ranges studied using traditional methods of time-resolved spectroscopy. Ultrafast extreme ultraviolet (XUV) absorption was used to KARL N. BLODGETT, TIMOTHY S. ZWIER, Department of Chemistry, Purdue University, West Lafayette, investigate electron and hole dynamics in perovskites by observing transitions from core level (I 4d and Br 3d ) to the valence IN, USA. and conduction bands. Using a table-top instrument, ultrashort (30 fs) pulses of XUV radiation with a broad spectrum (40-75 We present laser-desorbed, jet-cooled, conformation-specific UV and IR data on a series of increasingly complex eV) were generated via high-harmonic generation. Transient absorption measurements using visible pump and XUV probe β-peptide oligomers: Ac-(ACHC)2-NHBn, Ac-ACHC-m4ACHC-NHBn, Ac-m5ACHC-m4ACHC-NHBn, Ac-m4ACHC- directly observed carrier and element specific relaxation dynamics in mixed-halide and layered perovskites for above band ACHC-NHBn, Ac-m4ACHC-m5ACHC-NHBn, Ac-(ACHC)3-NHBn, and Ac-(ACHC)4-NHBn. Synthetic foldamers edge excitation in the femtosecond and picosecond time scales. are polymers composed of non-natural building blocks which either mimic, or expand upon, nature’s preferred sec- ondary structures which are accessible to pure α-amino acid sequences. The ring-constrained β-amino acid, cis-2- aminocyclohexanecarboxylic acid (ACHC), is one such non-natural building block which when polymerized with alternating TK03 2:21 – 2:36 chirality has been shown to adopt both right- and left-handed 12/10 mixed helices in solution and crystalline form. ACHC MOS may adopt two local minima conformations: one in which the NH is axial (ax) with respect to the cyclohexane chair and DIRECT DETERMINATION OF BAND GAP RENORMALIZATION IN PHOTO-EXCITED MONOLAYER 2 the C=O is equatorial (eq), and vice versa. In poly-ACHC sequences, the cooperative conformational isomerization between FANG LIU, MARK E ZIFFER, KAMERON R HANSEN, JUE WANG, XIAOYANG ZHUa, Chemistry, these two minima switches the screw-sense of the 12/10 helix. The use of the more rigid β-amino acids, cis-2-amino- Columbia University, New York, NY, USA. cis-4-methylcyclohexanecarboxylic acid (m4ACHC) and cis-2-amino-cis-5-methylcyclohexanecarboxylic acid (m5ACHC) sterically lock the ACHC residue into one of its two minima, depending on the stereochemical patterning at the ring’s three A key feature of monolayer semiconductors, such as transition-metal dichalcogenides, is the poorly screened Coulomb stereocenters. The isolated, solvent-free conformational preferences will be compared with condensed phase data, and the potential, which leads to large exciton binding energy (Eb) and strong renormalization of the quasiparticle bandgap (Eg)by energetic impact of the benzyl chromophore on preferred structure will be discussed. carriers. The latter has been difficult to determine due to cancellation in changes of Eb and Eg, resulting in little change in optical transition energy at different carrier densities. Here we quantify bandgap renormalization in macroscopic single crystal MoS2 monolayers on SiO2 using time and angle resolved photoemission spectroscopy (TR-ARPES) with femtosecond extreme UV (EUV) probe. At excitation density above the Mott threshold, Eg decreases by as much as 360 meV. We compare the carrier density dependent Eg with previous theoretical calculations and show the necessity of knowing both doping and excitation densities in quantifying the bandgap.

aTo whom correspondence should be addressed. E-mail: [email protected] 124 125

TK04 2:39 – 2:54 TK06 3:51 – 4:06 RAPID HOLE COOLING AND SLOW ELECTRON COOLING IN METHYLAMMONIUM LEAD IODIDE PER- CHARGE CARRIER DYNAMICS OF ANATASE TiO2 PROBED BY EXTREME ULTRAVIOLET REFLECTION- OVSKITE ABSORPTION SPECTROSCOPY

MAX A VERKAMP, AASTHA SHARMA, JOSH VURA-WEIS, Department of Chemistry, University of Illi- EMILY B HRUSKA, JAKUB HUSEK, ROBERT BAKER, Department of Chemistry and Biochemistry, The nois at Urbana-Champaign, Urbana, IL, USA. Ohio State University, Columbus, OH, USA.

Methylammonium lead iodide perovskite is a promising candidate for next-generation photovoltaics. One application for Materials with improved catalytic efficiency can be designed based on a more thorough understanding of the excited this perovskite is in hot-carrier collection devices. In a standard cell any excess energy from absorbed photons is lost as heat, state dynamics that mediate energy transfer and drive charge separation. High harmonic generation can produce ultrafast but a cell can be designed to extract carriers before they cool to increase its efficiency above the Shockley-Queisser limit. In pulses in the extreme ultraviolet (XUV) region, enabling the use of XUV reflection-absorption (XUV-RA) spectroscopy to order to achieve this, the cooling rate of carriers must be sufficiently slower than the extraction time. Perovskite may fit this analyze signatures of photoexcited electrons and holes separately. From XUV-RA experiments on anatase TiO, it is shown criterion due to the presence of a hot-phonon bottleneck for carrier cooling. Time-resolved XUV absorption from the core I4d that, for the first 800 fs after photoexcitation there is an apparent quantum beating at 417 cm−1. This frequency is consistent level to the valence band (45-50 eV) after optical excitation (3.1 eV) was used to probe the hole distribution of photoexcited with coupling between a free carrier state and a large polaron state, which has been previously observed in TiO2. Following perovskite. The holes were found to cool rapidly (cooling time shorter than 400 fs) at high carrier density (1019 cm−3). In the initial dynamic equilibrium between these two states, the electron localizes to a more energetically stable Ti3+ defect comparison, time-resolved optical absorption (1.5-2.5 eV) was used to probe the electron distribution, which was found to state 1 eV below the conduction band within 1.22 ps. We hypothesize that the strong electron-phonon coupling leading to cool slowly (cooling time longer than 5 ps) for the same excitation density. This indicates that a hot-carrier collection device the observed beating may be the result of Ti3+ defect states which we show are prevalent in this material. To investigate 3+ using perovskite should be designed to only extract hot electrons, not hot holes. this hypothesis, we are now performing measurements on stoichiometric TiO2 with Ti defects removed. These ongoing 3+ experiments on defect-free TiO2 will provide a more complete understanding of the role the Ti defects play in the charge carrier kinetics of this catalytically relevant material.

TK07 4:09 – 4:24 ELEMENT-SPECIFIC MEASUREMENT OF HOLE TRANSPORT IN A Ni-TiO2-Si PHOTOLECTRODE USING TRAN- SIENT EXTREME ULTRAVIOLET SPECTROSCOPY

SCOTT KEVIN CUSHING, Chemistry and Chemical Engineering, California Institute of Technology, Intermission Pasadena, CA, USA.

A passivating oxide layer is critical for the stability and the performance of solar-fuel photoelectrodes. While the semi- conductor surface can be passivated by a few nanometer oxide film, the best performance often correlates with a thicker and TK05 3:33 – 3:48 defect-rich amorphous TiO2 layer. The defect states are suggested to facilitate hole transport between the semiconductor and metal catalyst. In this presentation, transient extreme ultraviolet (XUV) absorption spectroscopy quantifies the electron ACHIEVING SURFACE SENSITIVITY IN ULTRAFAST XUV SPECTROSCOPY and hole transport between each element of a photoexcited Ni-TiO2-Si photoelectrode. A ballistic hole tunneling from the ROBERT BAKER, SOMNATH BISWAS, JAKUB HUSEK, STEPHEN LONDO, Department of Chemistry and p-type Si to the Ni metal is measured in 100 fs after photoexcitation of the Si. The measured hole injection efficiency is 26%. Biochemistry, The Ohio State University, Columbus, OH, USA. The transient hole population is then measured to back-diffuse through the TiO2 on a picoseconds timescale, followed by an increased electron-hole recombination at the Si-TiO2 interface. By temporally resolving the population of electrons and holes The ability to follow electron dynamics at surfaces is necessary to identify the material properties and surface defect in each layer of the junction, the hole transport velocity in the TiO2, the hole mobility in the Si, the diffusion constant of holes states, which mediate carrier lifetime and ultimately determine energy conversion efficiency. Toward this goal we have in the TiO2, and the surface recombination velocity at the Si/TiO2 interface are quantized. recently developed extreme ultraviolet reflection-absorption (XUV-RA) spectroscopy as a surface specific analog of XUV transient absorption. Unlike absorption measurements, which sample only the imaginary component of the refractive index, TK08 4:27 – 4:42 reflection measurements probe both the real and imaginary components of the material’s complex refractive index. We DIRECT OBSERVATION OF EXCITON DISSOCIATION AND CHARGE INJECTION: THE FIRST-STEP IN SOLAR find that the imaginary component is sensitive to the chemical state of the material as reported by the core-hole resonant ENERGY CONVERSION TECHNOLOGIES spectrum while the real component is additionally sensitive to the physical morphology of the material. Using semi-empirical spectral simulations we show that XUV-RA spectroscopy retains the element and chemical state specificity of XUV absorption SOMNATH BISWAS, JAKUB HUSEK, STEPHEN LONDO, ELIZABETH A FUGATE, ROBERT BAKER, spectroscopy. Accordingly, this technique extends the benefits of element specific x-ray absorption spectroscopy to the Department of Chemistry and Biochemistry, The Ohio State University, Columbus, OH, USA. study of surface electron dynamics by measuring core-hole resonances with a probe depth of less than 3 nm and a time resolution of less than 100 fs. Here we describe the application of XUV-RA spectroscopy to the study of ultrafast electron Understanding the mechanism of interfacial hole transfer and the chemical nature of the hole acceptor state in NiO based trapping and defect-mediated recombination at the surface of NiO. Direct observation of ultrafast electron trapping and solar materials are important for the rational design of devices with improved efficiency. NiO is widely utilized as a hole subsequent recombination shows that grain boundaries rather than oxygen vacancies are responsible for fast electron-hole transport layer in solar energy devices. However, due to its complex electronic structure, the chemical nature of the hole pair recombination. This result clarifies the design parameters for NiO water oxidation catalysts by showing that oxygen acceptor state has remained an open question, despite the fact that hole localization in NiO significantly influences device vacancies, which enhance catalytic activity, have no detrimental effect on carrier lifetime. Rather, carrier lifetime can be efficiency. To comment on this, we present results of ultrafast charge carrier dynamics in a NiO based model heterojunction (Fe2O3/NiO) using extreme ultraviolet reflection-absorption (XUV-RA) spectroscopy. Element specific XUV-RA demon- dramatically extended by the elimination of near-surface grain boundaries even in the presence of chemically active oxygen 3+ vacancies. strates the formation of transient Ni within a few ps following selective photoexcition of the underlying Fe2O3 substrate. This indicates that fast hole transfer in this system occurs to NiO valence band states composed of significant Ni 3d character. Additionally, we show that this hole injection process proceeds via a two-step sequential mechanism where fast field driven exciton dissociation occurs in Fe2O3 in 680 ± 60 fs, followed by subsequent hole injection to NiO in 9.2 ± 2.9 ps. These results reveal the chemical nature of the hole acceptor state in widely used NiO hole transport layers and provides a direct observation of exciton dissociation and interfacial hole transfer in this system. 126 127 TL. Spectroscopy as an analytical tool Tuesday, June 18, 2019 – 1:45 PM TK09 4:45 – 5:00 Room: 2079 Natural History ULTRAFAST X-RAY MULTI-EDGE SPECTROSCOPY WITH 100kHz OPCPA-DRIVEN HIGH HARMONIC GENERA- TION SOURCE Chair: Brandon Carroll, Harvard-Smithsonian Center for Astrophysics, Cambridge, MA, USA

ELIO G CHAMPENOIS, AMY CORDONES-HAHN, JAMES P CRYAN, THOMAS JA WOLF, Stanford TL01 1:45 – 2:00 PULSE Institute, SLAC National Accelerator Laboratory, Menlo Park, CA, USA. SAMPLING REQUIREMENTS FOR MIXTURE ANALYSIS USING MOLECULAR ROTATIONAL RESONANCE SPECTROSCOPY Time-resolved inner shell absorption spectroscopy is a sensitive and localized probe of valence electronic dynamics. By measuring the temporal evolution of near-edge absorption features of multiple atoms simultaneously, complex dynamics can JUSTIN L. NEILL, ALEX MIKHONIN, MATT MUCKLE, ROGER L REYNOLDS, BrightSpec Labs, Bright- be separated into the individual underlying processes. In the condensed phase, the migration of both electrons and holes Spec, Inc., Charlottesville, VA, USA. can be tracked during photoinduced interfacial electron transfer between a Ruthenium (Ru) metal complex and a copper oxide (CuO) substrate via transient absorption measurements at the various molecular and substrate specific atomic edges. Over the past few years, a number of studies have been performed that show the capability for gas-phase molecular A femtosecond water window source spanning the Carbon, Nitrogen, and Oxygen K-edges can also be used to follow the rotational spectroscopy to perform quantitative mixture analysis. In particular, the ability of this technique to identify new valence electronic dynamics and concerted nuclear motion of UV excited molecules such as nitrobenzene. We report progress compounds in a mixture on the basis of comparison to electronic structure theory is extremely powerful. For a number of on our development of such a source based on high harmonic generation (HHG) driven by a 100 kHz, >100 W optical chirped reasons, however, the sample introduction and volatilization methods employed warrant new development. First, mixtures pulse parametric amplifier and transient absorption measurements of the above systems. often contain components with different vapor pressures, and so care is required in extrapolating concentration information from observed signals.a Additionally, operator-to-operator variability, measurement cycle time, and ease of use are factors that should be considered. We will discuss our efforts to develop sampling interfaces to enable routine quantitative mixture analysis using molecular rotational spectroscopy, as well as challenges that the field still faces.

aC. West et al., ”Analysis of pear ester flavoring samples using broadband rotational spectroscopy,” 2018 International Symposium on Molecular Spectroscopy, talk RH06.

TL02 2:03 – 2:18 STRONG FIELD COHERENCE BREAKING AS A TOOL FOR IDENTIFYING ROTATIONAL TRANSITIONS DUE TO METHYL ROTOR STATES: 2-HEXANONE

SEAN FRITZ, PIYUSH MISHRA, TIMOTHY S. ZWIER, Department of Chemistry, Purdue University, West Lafayette, IN, USA.

As energy demands increase, more sustainable alternatives to finite fossil fuels need to be explored. Ketones are an important constituent in biomass derived liquids and small methyl ketones have high octane numbers and show low emissions of soot, yet, their combustion chemistry remains relatively unexplored. 2-hexanone is an interesting candidate as it has a long alkyl chain supporting numerous conformational isomers as well as a methyl rotor. In this study, the rotational spectrum of 2-hexanone was recorded over the 8-18 GHz region using a chirped pulse Fourier transform microwave (CP-FTMW) spectrometer. Strong field coherence breaking (SFCB) was utilized to selectively modulate rotational transitions belonging to the two lowest energy conformers of 2-hexanone, aiding the assignment. In addition, the SFCB method was applied for the first time to identify rotational transitions built off the two lowest energy hindered methyl rotor states of each conformer, 0a1 and 1e. Since these two states have rotational energy levels with different nuclear spin symmetries, their intensities could be selectively modulated by the resonant monochromatic pulses used in the SFCB method. The difference spectra, final fit and structural parameters will be discussed for all three conformers assigned.

TL03 2:21 – 2:36 DETECTION OF TRACE AMOUNT OF WATER IN VOLATILE ORGANIC COMPOUNDS BY A K-BAND MOLECU- LAR ROTATIONAL RESONANCE SPECTROSCOPY

SANDEEP C SINGH, SYLVESTRE TWAGIRAYEZU, Chemistry and Biochemistry, Lamar University, Beau- mont, TX, USA; MATT MUCKLE, ALEX MIKHONIN, JUSTIN L. NEILL, BrightSpec Labs, BrightSpec, Inc., Charlottesville, VA, USA.

Trace amount of water has been detected in ethanol (CH3CH2OH) and methanol (CH3OH) using a K-Band BrightSpec Microwave Rotational Resonance (MRR) spectrometer in the 18-26 GHz frequency range. The design of this instrument is based on segmented Chirped Pulse Fourier Transform microwave wave (CP-FTMW) spectroscopy, which exploits recent advances in digital electronics to allow fast measurement of broadband rotational spectra of polar molecules. The analysis of the observed rotational spectra reveals the presence of a weak rotational line shape of water due to sensitivity of MRR to polar volatile organic compounds . The capability for K-band MRR to extract water in a such chemical environment has been further examined and validated by spiking samples with known small amount of water. The resulting linear curves allowed the determination of limit of detections at ppm level. These findings suggest that K-band MRR has potential to be useful as a spectroscopic tool for fast detection of water in volatile organic compounds or other raw materials. 128 129

TL04 2:39 – 2:54 TL07 4:09 – 4:24 COMPARATIVE STUDIES OF PHOTO PHYSICAL PROPERTIES OF SOME COUMARINS : SOLVENTS AND SUB- ROTATIONAL SPECTROSCOPY OF FLAVOR COMPOUNDS IN PEACH BRANDY FOR PROCESS MONITORING IN STITUENTS EFFECT. CRAFT DISTILLERIES

SANJAY KUMAR, physics department, rajdhani college, university of delhi, delhi, delhi, india. CHANNING WEST, THOMAS MILLER, NOAH KHAN-RAFII, EMILY PLUNKETT, ALEXANDER CHMIELINSKI, JOHN HURST, THOMAS DELANEY, CHARLES PRESTON, BROOKS PATE, Department This paper reports the solvent and substituent effects on the electronic absorption and fluorescence emission spectra of of Chemistry, The University of Virginia, Charlottesville, VA, USA;JUSTINL.NEILL,BrightSpec Labs, Bright- 7- NH2, 7-Cl, 7-Br & 7-OH 4-CF3 Coumarin derivatives having different substituents at seven position in various solvents Spec, Inc., Charlottesville, VA, USA; ROBIN A. FELDER, Department of Pathology, The University of Virginia, (Polar and Non-Polar). The first excited singlet state dipole moment and ground state dipole moment were calculated using Monte Piccolo Farm and Distillery, Charlottesville, VA, USA. Bakhshiev, Kawski-Chamma-Viallet and Reichardt-Dimroth equations and were compared for all the Coumarin studied. In all cases the dipole moments were found to be higher in the excited singlet state then in the ground state indicating a substantial The feasibility of using molecular rotational spectroscopy as an on-line monitoring system for brandy distillation has redistribution of π- electron density in the excited state. The effect of different substituent at seven position was interpreted in been investigated in collaboration with Monte Piccolo Farm and Distillery. The target product is brandy produced from terms of the calculated values of excited singlet state and ground state dipole moment. The angle between the excited singlet Indian Blood peaches. A previous study identified key flavor components from 18 peach cultivars, and lactones in the C8–C12 state and ground state dipole moment is also calculated. The red shift of the absorption and fluorescence emission bands, size range appear to produce much of the characteristic peach flavor.a These lactones are present in different ratios across observed for all the Coumarins studied upon increasing the solvent polarity, indicating that the electronic transitions were π peach cultivars and, as a result, these ratios may help identify the ideal peach for brandy distillation. Rotational spectra of → π* nature. Kamlet–Taft and Catalan solvent parameters were used to analyze the effect of solvents on all the Coumarins octa-, deca-, and dodecalactone isomers were collected to provide a library of possible flavor congeners. Experimental spectra which was interpreted in terms of solute–solvent interaction and specific interactions. of the lactones were in good agreement with dispersion corrected density functional theory calculations.b Despite the lactones possessing long alkyl tails, conformational populations observed in the pulsed-jet expansion were dominated by one or two conformations. A lab-prepared mixture of peach flavor compounds and commercial peach extracts were analyzed to test the ability of the technique to analyze complex mixtures, similar to what would be seen during distillation. These measurements TL05 2:57 – 3:12 use temperature-programmed broadband rotational spectroscopy to separate the full spectrum of all mixture compounds into SPECTROSCOPIC TREASURE IN FORGOTTEN DATA: ROTATIONAL SPECTRUM ANALYSIS THROUGH AGGRE- a spectrum for each compound. Rapid monitoring of these flavor components with a cavity-enhanced Fourier transform GATED DATABASES microwave spectrometer using a pre-programmed sample profile has been demonstrated on the commercial instrument from BrightSpec that is based on the NIST compact Balle-Flygare spectrometer design.c MATT MUCKLE, JUSTIN L. NEILL, DAVE McDANIEL, ALEX MIKHONIN, BrightSpec Labs, BrightSpec, aXi, W.; Zheng, Q.; Lu, J.; Quan, J., Horticulture Plant Journal 3, 1-12 (2017). Inc., Charlottesville, VA, USA. bS. Grimme and M. Steinmetz, Phys. Chem. Chem. Phys. 15, 16031-16042 (2013). cR.D. Suenram, J.U. Grabow, A. Zuban, and I. Leonov, Rev. Sci. Instrum. 70, 2127-2135 (1999). We present the automated analysis of rotational spectra using archived experimental and ab initio data. Modern rotational spectroscopy techniques have made acquiring experimental data extremely fast, yielding many GHz of information in seconds. This is in contrast to the analysis, which still takes many hours if not weeks of an expert’s time to fit. In order to bring rotational spectroscopy to a wider audience, new applications, and enable new science, the effort and time required to analyze a spectrum needs to be reduced. TL08 4:27 – 4:42 To reduce the analysis time, we aggregated more than 200 experimental spectra (from local instruments and literature) 3 + TIME-RESOLVED POPULATIONS OF N2(A Σ ,v) IN NANOSECOND PULSE DISCHARGE PLASMAS and more than 16,000 ab initio calculations into a library that is leveraged by automated algorithms to screen for identifica- u tions in rotational spectra. Screening with experimental data has been shown to give both highly accurate identification and ELIJAH R JANS, KRAIG FREDERICKSON, Department of Aerospace and Mechanical Engineering, The Ohio quantification of a sample within a mixture in under 10 seconds per analysis. Unmatched residual lines are presented to the State University, Columbus, OH, USA; TERRY A. MILLER, Department of Chemistry and Biochemistry, The user for further analysis. Work is in progress to expand the number of matchable spectra inside the database and identify Ohio State University, Columbus, OH, USA; IGOR V. ADAMOVICH, Department of Aerospace and Mechanical unknown constants using ab initio databases. Engineering, The Ohio State University, Columbus, OH, USA.

3 + Absolute time-resolved populations of N2(A Σu ) excited electronic state generated in a repetitive ns pulse discharge in nitrogen have been measured by Cavity Ring Down Spectroscopy (CRDS) and Tunable Diode Laser Spectroscopy (TDLAS). 3 + TL06 3:15 – 3:30 CRDS measurements of N2(A Σu ,v=0-2) populations are made in the discharge afterglow at a pressures of 10-40 Torr. The AUTOMATED, CONTEXT-FREE ASSIGNMENT OF ASYMMETRIC ROTOR MICROWAVE SPECTRA data reduction procedure takes into account the linewidth of the pulsed laser source, comparable with the absorption linewidth 3 + and resulting in a non-single exponential ring down decay. Peak N2(A Σu ,v=0,1) populations after a 10-pulse ns discharge LIA YEH, LINCOLN SATTERTHWAITE, DAVID PATTERSON, Physics, University of California, Santa Bar- burst are 1.5x1011 cm−3. In the afterglow, these populations exhibit a relatively slow decay with the characteristic time of bara, CA, USA. approximately 500 μs, most likely due to the quenching by the N2 molecules in the ground electronic state. TDLAS data 3 + have been taken at a higher pressure of 130 Torr. Absolute time-resolved N2(A Σu ,v=0,1) number densities are measured We present a new algorithm, Robust Automated Assignment of Rigid Rotors (RAARR), for assigning rotational spectra during ns pulse discharge bursts up to 25 pulses long and in the afterglow, peaking at 5x1012 cm−3 and 3x1013 cm−3.The of asymmetric tops. The RAARR algorithm can automatically assign experimental spectra under a broad range of conditions, 3 + results indicate that N2(A Σu ) is generated after every discharge pulse on a 20-50 μs time scale, much longer compared including spectra comprised of multiple mixture components, in about 100 seconds or less. The RAARR algorithm exploits to the discharge pulse duration, and decays between the pulses. The decay rate increases during the discharge burst. In the constraints placed by the conservation of energy to find sets of connected lines in an unassigned spectrum. The highly 3 + afterglow, N2(A Σu ,v=0,1) populations decay significantly more rapidly compared to the low-pressure CRDS conditions, constrained structure of these sets eliminates all but a handful of plausible assignments for a given set, greatly reducing the with the characteristic time of approximately 100 μs. The results demonstrate that both CRDS and TDLAS diagnostics number of potential assignments that must be evaluated. We successfully apply our algorithm to automatically assign 15 3 + can be used for time-resolved, absolute N2(A Σu ) measurements in transient nonequilibrium plasmas and the afterglow, experimental spectra, including 5 previously unassigned species, without prior estimation of molecular rotational constants. with the detection limit of ≈ 1010 cm−3. The data obtained using these two diagnostics are complementary, since TDLAS In 9 of the 15 cases, the RAARR algorithm successfully assigns two or more mixture components. 3 + measurements can be used at the conditions when the N2(A Σu ) populations may be too high, or vary too rapidly for accurate CRDS measurements. Intermission 130 131 WA. Astronomy TL09 4:45 – 5:00 Wednesday, June 19, 2019 – 8:30 AM MACHINE LEARNING APPLIED TO RAMAN SPECTRA OF PANCREATIC CANCER CELLS TO IDENTIFY MOLEC- Room: 116 Roger Adams Lab ULAR SIGNATURES, PATTERNS AND PROTEIN EXPRESSIONS. Chair: Michael C McCarthy, Harvard-Smithsonian Ctr for Astrophysics, Cambridge, MA, USA CHRISTOPHER MANDRELL, Physics, Southern Illinois University Carbondale, Carbondale, IL, USA; SAKINEH E.M. ABADI, FARHAN CHOWDHURY, Mechanical Engineering and Energy Processes, Southern Illinois University-Carbondale, Carbondale, IL, USA; P SIVAKUMAR, Physics, Southern Illinois University Carbondale, Carbondale, IL, USA. WA01 8:30 – 8:45 Pancreatic cancer is the third leading cause of cancer-related deaths in the United States, with the life expectancy for patients diagnosed in the late stage ranging from 6-12 months. This study is part of a group effort to examine the hypothesis FORMATION OF INTERSTELLAR C60 FROM SILICON CARBIDE CIRCUMSTELLAR GRAINS that, difficult to detect, tumor initiating cells (TIC) exist in small numbers in the solid tumors and are responsible for the JACOB BERNAL, Department of Chemistry and Biochemistry, University of Arizona, Tucson, AZ, USA;LUCY cancer’s progression and relapse. The pancreatic cell line MIA PaCa-2 is seeded and grown in 90 Pa 3D fibrin gels for M. ZIURYS, Department of Chemistry and Biochemistry, Department of Astronomy, The University of Arizona, 10 days then samples are collected and Raman spectra obtained from a 784nm laser in the 150-1800nm and 2500-3500nm Tucson, AZ, USA; PIERRE HAENECOUR, Department of Planetary Science, Lunar and Planetary Laboratory, ranges. These spectra are analyzed via combinations of data preprocessing, wavelength or dimension reduction and machine University of Arizona, Tucson, AZ, USA; JANE HOWE, Department of Materials Science and Engineering, learning classification algorithms. We extend to other cell lines such as CFPAC-1 and PANC-1. Support vector machine University of Toronto, Toronto, Canada; THOMAS J. ZEGA, Department of Planetary Science, Lunar and (SVM) and k-nearest neighbors (kNN) supervised machine learning classifiers are applied to the raw and pre-processed data Planetary Laboratory, University of Arizona, Tucson, AZ, USA; SACHIKO AMARI, Physics Department and sets and with various statistical and machine learning dimension reduction protocols. These combinations are compared to McDonnell Center for the Space Sciences, Washington University in St. Louis, St. Louis, MO, USA. determine which performed best at classifying cancer and normal cell samples, and which led to selection of the same or similar dimensions. Identification of the best performing dimensions/wavelengths is then attempted from the Raman spectra The positive detection of buckminsterfullerene (C60) in circumstellar and interstellar environments has changed by comparing them to existing biological molecule Raman databases to identify the patterns in the spectra and any unique paradigms of chemical complexity in the hostile conditions of space. While C60 is a significant sink of interstellar carbon, molecular signatures or protein expressions that could prove useful to better understanding and therefore treating pancreatic the formation mechanism is still the subject of speculation. To examine C60 formation, we have conducted shock-heating cancer. experiments on synthetic, 3C-SiC grains, the most common polytype generated by stars. Measurements of the heated grains, conducted with transmission electron microscopy (TEM) and electron energy-loss spectroscopy (EELS) techniques, show the TL10 5:03 – 5:18 formation of graphite and carbon nanobuds on the sample surface. The nanobud diameters are nearly identical to that of C60, POPULATION ENHANCEMENT AND ROTATIONAL CHARACTERIZATION OF GAUCHE-ISOPRENE BY HIGH indicating that spherical structures may be forming as well. These data suggest that C60 is formed by the shock-heating of RESOLUTION FTMW SPECTROSCOPY common SiC grains at the end of the asymptotic giant branch (AGB) phase. In addition, TEM measurements of actual pre- solar grains extracted from meteorites show a central SiC core, surrounded by graphite, confirming our proposed formation JESSIE P PORTERFIELD, Radio and Geoastronomy Division, Harvard-Smithsonian Center for Astrophysics, mechanism. Cambridge, MA, USA; J. H. WESTERFIELD, Department of Chemistry, The University of California, Davis, CA, USA; LINCOLN SATTERTHWAITE, DAVID PATTERSON, Physics, University of California, Santa Barbara, CA, USA; BRYAN CHANGALA, JILA, National Institute of Standards and Technology and Univ. of Colorado Department of Physics, University of Colorado, Boulder, CO, USA; JOSHUA H BARABAN, Chemistry, Ben- WA02 8:48 – 9:03 Gurion University of the Negev, Beer-Sheva, Israel; MICHAEL C McCARTHY, Atomic and Molecular Physics, Harvard-Smithsonian Center for Astrophysics, Cambridge, MA, USA. TOWARDS A MECHANISM FOR FORMATION OF SILICON CARBIDE CRYSTALS IN AGB STARS

Isoprene is a highly abundant species in the atmosphere, second only to JESSE J LUTZ, Department of Engineering Physics, Air Force Institute of Technology, Wright-Patterson AFB, methane in hydrocarbon emissions. There are two stable conformers of iso- OH, USA; XIAOFENG F DUAN, DoD Supercomputer Resource Center, Air Force Research Laboratory, Wright- Patterson AFB, OH, USA; LARRY W BURGGRAF, Department of Engineering Physics, Air Force Institute of prene, trans and gauche, and due to the fact the ground state trans is highly 600 Temp (K) abundant at room temperature (97%), its microwave spectrum has been known 300 Technology, Wright-Patterson AFB, OH, USA. since the 1960’s. The gauche conformer, however, has evaded microwave ob- 500 350 Silicon carbide (SiC) grains comprise a significant fraction of the dust found around carbon-rich AGB stars. Their servation until now. We have characterized the rotational parameters for the 400 400 presence in the interstellar medium is thought to originate from self-assembly of organosilicon building blocks, including inversion states (0+/0−) of gauche-isoprene, aided by high levels of theory and 450 _ previously observed species such as carborundum and cyclic silicon dicarbide (c-SiC2). However, the actual formation two complementary, high resolution Fourier transform microwave (FTMW) 300 + 0 0 mechanisms of even these simple silicon-bearing organic molecules remains elusive. Here it is proposed that disilyne (Si2H2) techniques: cavity enhanced FTMW coupled to a pulsed discharge nozzle, and 200 gauche reacts barrierlessly with abundant acetylene (C2H2) on a spin-conserving potential to form C2Si2H4. This species has been chirped-pulse FTMW in a cryogenic buffer gas cell. Thermal enhancement Intensity / mV shown in experimental and theoretical studiesa to photoisomerize under UV irradiation resulting in the formation of several (from 1.7% up to 10.3%) of the gauche population of isoprene is demonstrated 100 trans species, one being a c-SiC2 precursor and another being a highly polar species capable of supporting a dipole-bound electron. with inlet temperatures ranging from 300-450 K in the cryogenic buffer gas cell. 0 This strongly dipolar C2Si2H4 isomer may represent the missing link supporting the molecular aggregation hypothesis for SiC This work demonstrates for the first time that the buffer gas cell is well suited 12.404 12.406 12.408 formation. Importantly, its polarity drives molecular aggregation, and, after subsequent oxidation to C2Si2, its heteronuclear for thermochemical studies similar to matrix isolation spectroscopy, but by far Frequency / GHz linkages are well-prepared for SiC nucleation, presumably initiated by a shock-wave pulsation event. Past theoretical studies simpler and more rapid analytical means. by our groupbc are combined with new results, computed at the DFT and coupled-cluster levels of theory, to support the proposed mechanism.

aLutz J.J., Inorganics, submitted bLutz J.J., Duan X.F., et al. J. Chem. Phys. 148, 174309 (2018) cByrd J.N., Lutz J.J., et al. J. Chem. Phys. 145, 024312 (2016) 132 133

WA03 9:06 – 9:21 WA06 10:36 – 10:51 IDENTIFICATION OF VO (X4Σ) IN THE ENVELOPE OF VY CMa: A NEW CIRCUMSTELLAR MOLECULE THE TRANSITION FROM DIFFUSE ATOMIC GAS TO MOLECULAR CLOUD IN TAURUS

JACOB BERNAL,LUCYM.ZIURYS,Department of Chemistry and Biochemistry, University of Arizona, Tuc- STEVEN FEDERMAN, JOHNATHAN S RICE, Physics and Astronomy, University of Toledo, Toledo, OH, USA; son, AZ, USA; ROBERTA M. HUMPHREYS, Minnesota Institute for Astrophysics, University of Minnesota, ADAM RITCHEY, , Eureka Scientific, Seattle, WA, USA; HWIHYUN KIM, , Gemini Observatory, La Serena, Minneapolis, MN, USA. Chile;JOHNH.LACY,Department of Astronomy, The University of Texas at Austin, Austin, TX, USA;PAULF GOLDSMITH, Jet Propulsion Laboratory, California Institute of Technology, Pasadena, CA, USA;NICOLAS We have confirmed a new circumstellar molecule, VO, observed in the envelope of the supergiant star, VY Canis Majoris, FLAGEY, , Canada–France–Hawaii Telescope Corporation, Kamuela, HI, USA; GREGORY N. MACE, DAVID using the Hubble Space Telescope (HST) with its Imaging Spectrograph (STIS). The molecule, a free radical, was detected in L. LAMBERT, W. J. McDonald Observatory and Department of Astronomy, University of Texas at Austin, Austin, two clumps in the ejecta of this star via its B-X electronic transition in the near-infrared. The spectra are clearly circumstellar TX, USA. as the lines are significantly red-shifted from the stellar velocity, and arise from material 40-50 R* from the star. Wallerstein had identified some of the observed lines previously towards VY CMa; our data prove their spatial location. The VO lines are We study four lines of sight that probe the transition from diffuse molecular gas to molecular cloud material in Taurus. likely excited by resonant scattering from the star through a hole in the dusty shell. Measurements of atomic and molecular absorption are used to infer the distribution of species and the physical conditions in the direction to stars behind the Taurus Molecular Cloud. New high-resolution spectra at visible and near infrared wavelengths + of interstellar K I,CH,CH ,C2, CN, and CO toward HD 28975 and HD 29647 are combined with published results for HD 27778 and HD 30122. Gas densities and temperatures are inferred from analyses of C2, CN, and CO excitation. Our 18 −2 results for HD 29647 are noteworthy in that the CO column density is 10 cm , our analysis of CO and C2 excitation reveal WA04 9:24 – 9:39 −3 a temperature of 10 K and densities of about 1000 cm , and the CO excitation and radiation temperatures are the same, more IDENTIFYING TITAN’S ATMOSPHERE – A LOOK AT HYDROCARBONS POTENTIALLY PRESENT IN THE AT- like emission-line studies of dark molecular clouds. Similar results arise from our chemical analysis leading to CN through MOSPHERE OF SATURN’S MOST INTERESTING MOON reactions involving the observed species CH and C2. The other directions are typical of molecule-rich diffuse clouds and can be considered CO-dark gas. DANIEL M. HEWETT, ANDY WONG, PETER F. BERNATH, Department of Chemistry and Biochemistry, Old Dominion University, Norfolk, VA, USA; BRANT E. BILLINGHURST, EFD, Canadian Light Source Inc., Saskatoon, Saskatchewan, Canada.

Much research in planetary atmospheres is focused on Titan, one of Saturn’s moons. This interest is driven by the Cassini- Hyugens mission and the fact that Titan’s atmosphere is considered a potential analog of prebiotic Earth. In order to identify the chemical composition of the moon’s atmosphere a catalog of known spectra is needed for accurate comparisons. The molecules of interest are small hydrocarbons, as they have been observed on Titan and can be generated via photochemistry of methane, a primary component of Titan’s atmosphere. This talk will look at propane, as well as new data that will be recorded for some of the larger possible hydrocarbons, such as neopentane, a molecule for which there is little data in the literature, and n-butane. Absorption cross sections were obtained for pure samples of propane and with hydrogen and helium broadening gases to simulate astronomical environments. The propane spectra were taken in the 3 micron region, at WA07 10:54 – 11:09 temperatures ranging from 200 to 298 K and at broadening gas pressures from 0 Torr to 300 Torr. Calibration of the cross EXO-PLANETARY HIGH-TEMPERATURE HYDROCARBONS BY EMISSION AND ABSORPTION SPEC- sections were carried out using data from the Pacific Northwest National Laboratory (PNNL) infrared database. TROSCOPY (e-PYTHEAS PROJECT)

VINCENT BOUDON, Laboratoire ICB, CNRS/Universite´ de Bourgogne, DIJON, France; ATHENA COUSTE- Intermission NIS, LESIA, Observatoire de Paris / CNRS / UPMC, Meudon, France; ALAIN CAMPARGUE, UMR5588 LIPhy, Universite´ Grenoble Alpes/CNRS, Saint Martin d’Heres,` France; ROBERT GEORGES, IPR UMR6251, CNRS - Universite´ Rennes 1, Rennes, France; VLADIMIR TYUTEREV, Laboratoire GSMA, CNRS / Universitede´ Reims Champagne-Ardenne, REIMS, France. WA05 10:18 – 10:33 MID-IR OBSERVATIONS OF THE LATE-TYPE STARS VY CMa AND o-CETI USING IRTF-TEXES AROUND 8 AND e-PYTHEAS is a multidisciplinary project which combines theoretical and experimental work with exoplanet modelling 10μm applications. It sits on the frontier between molecular physics, theoretical chemistry and astrophysics. It aims at enhancing our understanding of the radiative properties of hot gaseous media to allow for improved analysis and interpretation of the GUIDO W FUCHS, Institute of Physics, University Kassel, Kassel, Germany; DANIEL WITSCH, Institute of large mass of data available on the thousands of exoplanets and exoplanetary systems known to date. Our approach is to Physics, University of Kassel, Kassel, Germany; ALEXANDER A. BREIER, THOMAS GIESEN, Institute of use theoretical research validated by laboratory experiments and to then inject it into models of the atmospheres of the giant Physics, University Kassel, Kassel, Germany. gaseous planets in the solar system and other planetary systems. This will help to analyse data and address essential questions on the formation and evolution of planetary systems, such as retrieved by ESA’s M4 space mission ARIEL. Our consortium of Late-type stars eject large amounts of material into outer space. At the very beginning of this process, i.e. close to the 5 French laboratories and associated partners proposes to improve the existing high-temperature spectroscopy data for several star, atoms form small molecules which finally react further to form larger species like nanoparticles. This very first step molecular species detected in exoplanets. The provision of infrared (IR) laboratory data of methane, acetylene, ethylene and of chemical evolution is still not well understood. How do the first molecules form? What is the chemical inventory of ethane, between 500 and 2500 K will help to refine thermal profiles and provide information on the gaseous composition, the the stellar atmosphere? To investigate these processes in the vicinity of stars requires both, high spatial and high frequency hazes and their temporal variability. resolution. We have performed mid-infrared observations towards the stars VY Canis Majoris and Mira (o-ceti) using the high See the project’s website: http://e-pytheas.cnrs.fr resolution TEXES instrument at the IRTF observatory. As the identification of molecular species requires high confidence in the transition frequency positions accompanying laboratory measurements have been performed, e.g for Si2C, Al2OandTiO around 8 and 10 μm. 134 135 WB. Mini-symposium: Non-covalent Interactions WA08 11:12 – 11:27 Wednesday, June 19, 2019 – 8:30 AM ABSORPTION CROSS SECTIONS OF ISOBUTANE AND ITS POTENTIAL PRESENCE IN TITAN’S ATMOSPHERE Room: 100 Noyes Laboratory DANIEL M. HEWETT, DROR M. BITTNER, ANDY WONG, PETER F. BERNATH, Department of Chemistry and Biochemistry, Old Dominion University, Norfolk, VA, USA; BRANT E. BILLINGHURST, JIANBAO ZHAO, Chair: Josh Newby, Hobart and William Smith Colleges, Geneva, NY, USA EFD, Canadian Light Source Inc., Saskatoon, Saskatchewan, Canada; NICHOLAS LOMBARDO, CONOR A NIXON, Planetary Systems Laboratory, NASA Goddard Space Flight Center, Baltimore, MD, USA;DON JENNINGS, Instrument Systems and Technology Division, NASA Goddard Space Flight Center, Greenbelt, MD, USA.

The atmosphere of Titan, one of Saturn’s moons, is of great interest to the scientific community. With its primary components of nitrogen and methane, many believe Titan to be an analog of prebiotic Earth. The Cassini-Hyugens mission, launched in 1997, gathered massive amounts of data from both Saturn and Titan that is still being interpreted. Analysis of WB01 INVITED TALK 8:30 – 9:00 astronomical spectra is dependent on high-quality laboratory spectra. In the case of Titan this includes small hydrocarbons such as ethane, propane and benzene that are the products of photochemistry of methane. One complication that arises when NON-COVALENT INTERACTIONS ON THE BRINK OF CHEMICAL CHANGE making these assignments comes from incomplete or absent line-by-line spectroscopic data commonly used to determine KENNETH R. LEOPOLD, Chemistry Department, University of Minnesota, Minneapolis, MN, USA. molecular abundances. This problem can be avoided by utilizing absorption cross sections, as they are only dependent on the environment of the target molecule, environments that can be replicated in the lab. One of the molecules that potentially The study of weakly bound systems has been a multidimensional endeavor for over forty years. Beyond addressing exists on Titan is isobutane. This talk focuses on the absorption cross sections of isobutane needed for for Titan and the Giant the fundamental nature of intermolecular interactions, whose effects shape the world we live in, it has served as a platform Planets. Absorption cross sections were obtained for pure samples, and with hydrogen and nitrogen broadening gases. The for understanding the spectral consequences of large amplitude motions, developing the theory and practice of determining data were taken between 203 K and 295 K, at broadening gas pressures ranging from 0 Torr to 100 Torr, in the CH stretching intermolecular potentials, and elucidating the dynamics of photodissociation processes. In this talk, we emphasize the strong cm−1 cm−1 cm−1 region (2500-3280 ) and from 1050 to 1900 . Calibration of the cross sections were carried out using data connections between non-covalent and chemical interactions. We will trace work originating in the study of partially bound from the Pacific Northwest National Laboratory (PNNL) infrared database. These cross sections were then used to calculate Lewis acid-base complexes through investigations of proton transfer and, ultimately, to the discovery of carboxylic sulfuric an upper limit for isobutane in Titan’s atmosphere. anhydrides. Connections to modern problems in atmospheric chemistry are also emphasized.

WB02 9:06 – 9:21 THE CO–(D2O)2 AND CO–(D2O)3 COMPLEXES: INFRARED SPECTRA AND STRUCTURAL CALCULATIONS

A. J. BARCLAY, KOOROSH ESTEKI, Department of Physics and Astronomy, University of Calgary, Cal- gary, AB, Canada; ANDREA PIETROPOLLI CHARMET, Dipartimento di Scienze Molecolari e Nanosistemi, Universita` Ca’ Foscari, Venezia, Italy; BOB McKELLAR, Steacie Laboratory, National Research Council of Canada, Ottawa, ON, Canada; NASSER MOAZZEN-AHMADI, Physics and Astronomy/Institute for Quantum Science and Technology, University of Calgary, Calgary, AB, Canada.

The weakly-bound CO–(D2O)2 and CO–(D2O)3 complexes have been studied in the C-O stretching fundamental of the CO monomer. The van der Waals complexes are generated in a supersonic slit-jet apparatus and probed using a quantum cascade laser. One band was observed and analysed for each complex. The trimer, CO–(D2O)2, band is composed of a/b-type transitions establishing that the CO monomer lies nearly in the a-b inertial plane. The observed rotational constants lead to a small value of the inertial defect indicating that the heavy atoms in the trimer are co-planar. We observe no evidence of tunneling splitting and conclude that the large amplitude tunneling that exists in the free D2O dimer is quenched by the presence of the CO monomer. The CO–(D2O)3 band is also composed of a/b-type transitions establishing that the CO monomer lies nearly in the a-b inertial plane. Theoretical calculations were performed to find minima on the potential energy surfaces for both complexes at B2PLYP- D3BJ level of theory and applying counterpoise correction for the basis set superposition error. Further optimisations were then carried out at different coupled cluster levels of theory and extrapolating to the complete basis set limit. The rotational parameters at CCSD(T*)-F12c level of theory give results in very good agreement with those obtained from the observed spectra. In both complexes, the experimental structure corresponds to the lowest energy isomer. The corresponding bands for CO–(H2O)2 and CO–(H2O)3 are significantly predissociated which hampers their detailed rovibrational analysis. 136 137

WB03 9:24 – 9:39 WB05 10:00 – 10:15 THE COMPLICATED CONFORMATIONAL LANDSCAPES OF TETRAHYDRO-2-FUROIC DIMER AND MONOHY- ROTATIONAL SIGNATURES OF DISPERSIVE STACKING IN THE FORMATION OF AROMATIC DIMERS DRATE: BROADBAND ROTATIONAL SPECTRA AND COMPREHENSIVE CONFORMATIONAL SEARCHES MARIYAM FATIMA, AMANDA STEBER, FS-SMP, Deutsches Elektronen-Synchrotron (DESY), Hamburg, FAN XIE, NATHAN A. SEIFERT, MATTHIAS HEGER, WOLFGANG JAGER,¨ YUNJIE XU, Department of Germany; ANJA POBLOTZKI, Institute of Physical Chemistry, Georg-August-Universitat¨ Gottingen,¨ Gottingen,¨ Chemistry, University of Alberta, Edmonton, AB, Canada. Germany; CRISTOBAL PEREZ, SABRINA ZINN, MELANIE SCHNELL, FS-SMP, Deutsches Elektronen- Synchrotron (DESY), Hamburg, Germany. Tetrahydro-2-furoic acid (THFA), a chiral carboxylic acid which is often used as a precursor in syntheses of pharma- ceuticals, exhibits a complex conformational landscape in its monomeric form.1 Detailed analyses of its conformational Non-covalent molecular aggregate formation is dictated by inter- and intramolecular forces. The role of these interactions distribution and conversion barriers using rotational spectroscopy and theoretical modeling were reported recently.1 In the in stabilizing biological molecules is of great interest to many scientific communities. Characterizing these forces has also current study, we focus on investigated how intermolecular interactions with water and THFA itself influence the aforemen- gained a lot of importance for understanding grain formation in the interstellar medium, especially for aromatic systems such tioned conformational preference. A large number of initial conformational geometries were generated using a semiempirical as polycyclic aromatic hydrocarbons (PAHs).a Broadband rotational spectroscopy studies of weakly bound complexes are tight-binding (TB) quantum chemistry code, GFN-xTB, designed for prediction of equilibrium structural properties, such as able to accurately reveal the structures and internal dynamics of molecular clusters isolated in the gas phase. To understand geometries, vibrational frequencies, and non-covalent interactions.2 The final geometry optimizations were carried out at the the weak interactions in biological and astrochemical relevant molecules, we report here our studies on the homodimers of B3LYP-D3(BJ)/def2-TZVP, B3LYP-D3(BJ)/6-311++G(2d,p), and MP2/6-311G++(2d,p) levels of theory. Very interestingly, fluorene (C13H10), dibenzofuran ((C6H4)2O), and diphenylether ((C6H5)2O). While their structures show overall similarities, in the THFA monohydrate, the two monohydrates observed contain the most stable THFA monomeric conformer and are they differ in structural flexibility, planarity, and dipole moment. In order to determine the structure of the corresponding ranked the ninth and tenth in terms of their relative energy ordering. On the other hand, the THFA dimer observed contains homodimers, we targeted transitions in the 2-8 GHz range using broadband rotational spectroscopy. Our experimental results the third most stable monomeric conformers. We interpret the observed phenomena in terms of the conformational conversion show that all the observed homodimers are dominated by dispersion interactions such as CH-π or π-π, but the dibenzofuran barriers and conformational cooling effects. dimer is also influenced by repulsion between the free electron pairs of the oxygen atoms and the π clouds.b a A. L. Steber, et al., J. Phys. Chem. Lett., 8 (2017), 5744-5750. b M. Fatima et al., Angew. Chem. Int. Edit., 131 (2019), 3140.

Intermission

WB06 10:54 – 11:09 COLD ION SPECTROSCOPY OF PYRIDINIUM IONS: AN EXPERIMENTAL PROBE TO EVALUATE NON- WB04 9:42 – 9:57 COVALENT INTERACTIONS IN THE GAS PHASE CONFORMATIONAL LANDSCAPE OF 3-MERCAPTOPROPIONIC ACID AND METHYL 3- MERCAPTOPROPIONATE REVEALED BY MICROWAVE SPECTROSCOPY AND THEORETICAL CALCULATIONS ALEXANDRA TSYBIZOVA, VLADIMIR GORBACHEV, LARISA MILOGLYADOVA, PETER CHEN, De- partment of Chemistry and Applied Biosciences, ETH Zurich, Zurich, Switzerland. WESLLEYG.D.P.SILVA, JENNIFER VAN WIJNGAARDEN, Department of Chemistry, University of Mani- toba, Winnipeg, MB, Canada. Current quantum chemical methods, such as DFT and coupled-cluster excel at describing the physical properties of small molecular systems. However, they perform quite poorly when used to describe large molecules. We recently demonstrated the The structures of 3-mercaptopropionic acid (mpa) [HS-CH2-CH2-C(O)-OH] and methyl 3-mercaptopropionate (mp) generality of this problem when benchmarking different theoretical methods against experimental gas-phase bond dissociation [HS-CH2-CH2-C(O)-O-CH3] were investigated in the range of 8-18 GHz using both chirped pulse and cavity-based Fourier energies values. While theory and experiment agree for small systems, bigger molecules show a large discrepancy. This transform microwave spectrometers. One (mpa1) and two (mp1 and mp2) stable conformers were assigned in the rotational indicates that certain phenomena are size-intensive and others size-extensive, and that the currently available techniques do spectra for the acid and the ester compound, respectively. Despite our efforts, no other energy minima predicted by theory not treat all of the phenomena uniformly, which calls into question their transferability to large systems. To overcome this, we was experimentally observed in the spectra which could be a result of their high relative energies and/or small barriers to must first identify the origin of these difficulties. This will then inform the formulation of better, more accurate computation re-arrangement (relaxation to lower energy conformers). Splitting due to the presence of the methyl internal rotor in the strategies. ester species were observed in the rotational transitions of both mp1 and mp2. The latter also presents an additional splitting To shed light on the source of these discrepancies, we have designed an independent experiment, one which is not affected related to the torsional motion of the SH group around the C-C-S-H dihedral angle that allows the interconversion between by the common mass spectrometric “suspects” such as kinetic shifts. We have measured the infrared spectra of pyridines, two enantiomers of mp2. The observed rotational transitions for the acid and the ester were fit using the Pickett’s SPFIT and quinolones, and pyridinium dimers using a home-made, newly constructed cryogenic FT-ICR mass spectrometer. Our results the XIAM programs, respectively. The derived rotational parameters are well-determined and consistent with the quantum reveal that the N-H stretching frequency is an excellent probe to test the accuracy of the optimized geometry—and hence mechanical calculations performed at both DFT B3LYP-D3BJ and ab initio MP2 methods with the aug-cc-pVTZ basis set. dispersion interactions—as it is very sensitive to the spatial proximity of substituents. The pyridinium cations with pendant The higher stability of conformers mpa1 and mp1 is explained by the presence of an intramolecular SH...O=C interaction, substituents become exquisitely sensitive molecular torsion balances for the measurement of non-covalent interactions in investigated on the basis of the quantum theory of atoms in molecules (QTAIM) and the non-covalent interaction (NCI) the gas phase. In addition, we computed the differences in N-H-N frequency for the proton-bound pyridinium dimers and −1 analyses. obtained shifts within a range of 500 cm , depending on the method/basis-set combination used. IR spectroscopy in the gas phase hence can be used to determine which combination of method and basis-set gives the right answer and for what reasons. 138 139

WB07 11:12 – 11:27 WB10 12:06 – 12:21 MICROWAVE SPECTRUM OF A SUPERACID AND ITS MONOHYDRATE: TUNNELING AND LARGE AMPLITUDE EFFECT OF UREA ON WATER HYDROGEN-BOND NETWORK AND DENATURATION OF PROTEIN. MOTION IN CF3SO2OH AND CF3SO2OH-H2O SNEHA BANERJEE, SOHINI SARKAR, RAPTI GOSWAMI, PANKAJ MANDAL, Department of Chemistry, ANNA HUFF, NATHAN LOVE, CJ SMITH, KENNETH R. LEOPOLD, Chemistry Department, University of Indian Institute of Science Education and Research, Pune, Maharshtra, India. Minnesota, Minneapolis, MN, USA. Water is a natural solvent and plays a crucial role in many biological processes like enzyme activity, protein folding The triflic acid monomer (CF3SO2OH) and its 1:1 complex with water (CF3SO2OH-H2O) have been observed by and denaturation. Interfacial water has a significant effect on the protein’s internal structure and dynamics. To understand chirped-pulse and cavity Fourier transform microwave spectroscopy. A pair of tunneling states was identified in the rotational the protein-water interactions, it is essential to know the time scales characteristic of both local protein rearrangements and spectra for both species. For CF3SO2OH, the assignment of b-type spectra led to the direct measurement and experimental water dynamics within the solvation shell. Urea is a well-known denaturant for proteins. It has been proposed earlier that determination of the tunneling energy (ΔE = 52.96704(90) MHz). M06-2X/6-311++G(3df,3pd) calculations predict a 2.8 urea disrupts the water structureab, though there have also been reports of it being considered a structure enhancercd.The kcal/mol barrier for the tunneling motion of the hydroxyl proton rotating around the S-O bond through a transition state in molecular picture of how urea interacts with the water hydrogen bond network and thereby with the proteins is still unclear. ◦ which the O-H is oriented anti with respect to the CF3 group. A complete 360 scan of the hydroxyl proton around the S-O Time-resolved optical Kerr effect (OKE), and time-domain Terahertz Spectroscopy (THz-TDS) are powerful techniques to bond shows an additional transition state in the syn orientation resulting in a 6.2 kcal/mol barrier. In the CF3SO2OH-H2O study the hydrogen bonded structure and dynamics of complex aqueous systems, in the picosecond time scales. Here, we complex, spectral doublets were observed with an approximate 3:1 intensity ratio indicative of an equivalent exchange of the have used OKE, and THz-TDS to investigate the mechanism behind urea denaturation of lysozyme. protons in H2O resulting from rotation about its C2 axis. The proposed water motion is further supported by the quenching The OKE data reveals the effect of different concentrations of urea on aqueous lysozyme solutions. The temporal profiles of the spectral pairs for the asymmetrically deuterated CF3SO2OH-DOH complex. Despite the strong acidity of triflic acid, of the aqueous protein solutions are almost indistinguishable from that of pure water but the relaxation time obtained by fitting no evidence of protonation of the water was observed. the longer times show a drastic retardation of the water dynamics at the maximum protein concentration. On the other hand, the solvent dynamics in urea solutions slows down with an increase in urea concentration. The reduced spectral densities (RSDs) obtained show a marked decrease in amplitude between the urea-water and the urea-water-protein system. Although WB08 11:30 – 11:45 the shape of the RSDs resembles the bimodal character of urea solutions, the addition of protein brings down the amplitude LIF STUDY FOR THE VIBRONIC STRUCTURE OF PARA-FLUOROPHENOL...AMMONIA BINARY COMPLEX of the mode associated with the reorientational dynamics. This change is even more apparent at lower urea concentrations. A detailed analysis of these line shapes is required to elucidate the effect urea on the water hydrogen bond network and to map SOUVICK BISWAS, TAPAS CHAKRABORTY, Physical Chemistry, Indian Association for the Cultivation of out the structural changes occurring in the protein on the addition of urea. Science, Kolkata, India. aSacco, A.; Holz, M. J. Chem. Soc., Faraday Trans. 1997, 93,1101. bHammes, G. G.; Schimmel, P. R. J. Am. Chem. Soc. 1967,89, 442. Laser-induced fluorescence excitation (LIFE) and dispersed fluorescence spectra of a binary complex between p- cChitra, R.; Smith, P. E. J. Phys. Chem. B 2000, 104, 5854. fluorophenol (pFP) and ammonia (NH3) have been measured in a supersonic jet expansion. The measured spectra reveal dStumpe, M. C.; Grubmuller, H. J. Phys. Chem. B 2007,111, 6220. that para fluorine substitution, which is remote from the binding phenolic site, has a very pronounced effect on the inter- molecular vibrational features that appear in the LIFE spectrum. These features also differ significantly compared to those of the 1:1 pFP-H2O complex [1]. The most intense low-frequency feature is the fundamental of the intermolecular stretching mode (σ), which displays a long progression in the DF spectrum implying occurrence of significant distortion of geometry upon electronic excitation of the complex. In addition, the DF spectra display features of very low threshold for vibrational mixing in the excited state [2]. However, no direct evidence for proton/hydrogen transfer is revealed for vibronic excitation of the complex up to 11 level (822 cm−1) of the p-FP moiety. [1] D.P. Mukhopadhyay, S. Biswas, T. Chakraborty, J. Phys. Chem. A 120 (2016) 9159. [2] D.P. Mukhopadhyay, S. Biswas, T. Chakraborty, Chem. Phys. Lett. 674 (2017) 71.

WB09 11:48 – 12:03 FLUORESCENCE DYNAMICS OF EXCITED STATE PROTON TRANSFER IN SALICYLIC ACID: REVISITED

HIRDYESH MISHRA, Department of Physics, Banaras Hindu University, Varanasi, Uttar Pradesh, India.

Excited state intramolecular proton transfer (ESIPT) reaction in salicylic acid (SA) and its derivatives has been the subject of intense investigations. Due to its importance in photo-chemical and photo-biological reactions, ESPT reaction has been reviewed by many workers in number of molecular systems. These compounds are promising in the development of proton transfer lasers, photostabilisers and information storage devices at the molecular level. Like other carboxylic acids, SA also exists as a cyclic hydrogen bonded dimmer in the solid state, in non-polar solvents and in the gas phase at high concentrations. SA dimer is the smallest aromatic system in which both intra and inter molecular hydrogen bonding exist and thus constitute an ideal model to study both inter and intra molecular proton transfer in a single system. This system is found to be complicated due to the presence of two acidic protons, one on the carboxylic group and other on the phenolic group in each monomeric unit in dimmer, which are partially exchanged. The emission spectra of two rotamers and their dimers unfortunately overlap. As a results, there is no reliable studies on the excited electronic states of SA in the condensed phase. SA shows dual emission (UV and blue) in the non-polar as well as in the crystalline state. In the present work, photo physics and photochemistry of SA in crystalline (solid) state have been reinvestigated by both experimental and computational spectroscopic computational calculations technique. 140 141 WC. Instrument/Technique Demonstration Wednesday, June 19, 2019 – 8:30 AM WC04 9:24 – 9:39 Room: 1024 Chemistry Annex DIRECT INSITU MEASUREMENTS OF ABSOLUTE CARRIER ENVELOPE PHASE OF ULTRASHORT PULSES

Chair: Brooks Pate, The University of Virginia, Charlottesville, VA, USA DUKE A. DEBRAH, Chemistry, Wayne State University, Detroit, MI, USA; GIHAN BASNAYAKE, GABRIEL A. STEWART, Chemistry, Wayne State University, Detroit,, MI, USA;WENLI,Department of Chemistry, Wayne State University, Detroit, MI, USA.

Many interesting and important physical processes such as high-harmonic generation and coherent control are highly WC01 8:30 – 8:45 sensitive to the absolute Carrier Envelope Phase (CEP) of ultrashort laser pulses. Thus, the control and measurement of the A NEW E-BAND CHIRPED PULSE SPECTROMETER FOR CHEMICAL KINETICS APPLICATIONS CEP is of immense importance in strong field physics and chemistry. Even though the relative CEP can be measured with few existing technologies, a simple direct insitu technique has not been developed previously. Here we demonstrate a new BRIAN M HAYS, THEO GUILLAUME, THOMAS SANDOW HEARNE, OMAR ABDELKADER technique based on angular streaking that can achieve such a goal. The results have been compared directly with well-known KHEDAOUI, ILSA ROSE COOKE, DIVITA GUPTA, SEBASTIEN D. LE PICARD, ROBERT GEORGES, f-2f interferometer measurements. This new technique will assist the research on light-matter interactions involving ultrashort ABDESSAMAD BENIDAR, LUDOVIC BIENNIER, IAN R. SIMS, IPR UMR6251, CNRS - Universite´ Rennes pulses and improve attosecond metrology. 1, Rennes, France.

The E-band (60-90 GHz) is a useful spectral region for studying molecules that are highly reactive. Species that can be detected in this range include polyatomics with two or more heavy atoms. These species are particularly interesting as many WC05 9:42 – 9:57 products from chemical reactions fall within this range. Chirped pulse spectroscopy allows for these products to be detected MULTI-ANTENNAE DETECTION IN A CP-FTMW SPECTROMETER at fast timescales compatible with reaction kinetics measurements. To this end, we have constructed a new chirped pulse Fourier transform millimeter wave spectrometer operating within the E-band. The spectrometer uses a 300 mW high power FRANK E MARSHALL, AMANDA JO DUERDEN, NICOLE MOON, KRISTEN DONNELL, G. S. GRUBBS broadband amplifiers as well as a low noise receiver protected by a fast switch. The system has been tested with a range II, Department of Chemistry, Missouri University of Science and Technology, Rolla, MO, USA. of stable molecules both at low pressures and in the presence of rare gas colliders to simulate the experimental environment for reaction kinetics studies. The effects of collisions on spectra have been examined, with particular attention being given Recent experiments in the Grubbs research group at the Missouri University of Science and Technology have shown that to pressure broadening and quenching of the free induction decay. The description of this spectrometer as well as results it is possible to detect rotational spectra of molecules in a CP-FTMW using multiple horn antennae. This allows for increased from pressure broadening tests will be presented and applications towards detecting products of chemical reactions will be sensitivity by sampling a free induction decay twice, each at a separate point. Utilizing the traditional CP-FTMW design of discussed. two horns – one for transmitting and one for receiving – it was shown that it is possible to use the transmitting horn to also receive spectra. This is achieved by adding a circulator, switch, and low noise amplifier in the circuit between the transmitting horn and power amplifier. This has been demonstrated on OCS, 1,3-Difluorobenzene, and Chloroacetone in the 6-18 GHz region of the electromagnetic spectrum utilizing a variety of experimental setups. Results of these experiments as well as WC02 8:48 – 9:03 issues with implementing this setup, such as FID phasing issues and data analysis, will be discussed. PERFORMANCE OF A 6-18 GHZ DDS-BASED SEGMENTED CHIRP PULSE FOURIER TRANSFORM MICROWAVE SPECTROMETER 8 HALEY N. SCOLATI, ANNA L PISCHER, KELLY S. MEYER, J. H. WESTERFIELD, KYLE N. CRAB- 3 TREE, Department of Chemistry, The University of California, Davis, CA, USA. 2 4 4 5 6 7 Chirped pulse Fourier transform spectroscopy (CP-FTMW) has become a widely used technique for the detection of 1 5 Vacuum Chamber molecular rotational spectra owing to its broad frequency coverage. Traditional CP-FTMW set ups involve top-quality broad- band arbitrary waveform generators (AWG), high-power amplifiers, and digitizers, which are expensive due to their specifi- cations. Our group has designed a cost-effective 6-18 GHz segmented CP-FTMW broadband spectrometer coupled with a 6 direct digital synthesizer (DDS) (Finneran et al., Rev. Sci. Inst. 84, 2013, 083104 and Neill et al., Opt. Express, 21, 2013, 19743). In this talk, we will discuss the performance of this spectrometer used with a static waveguide cell to measure the rotational spectra of volatile polar molecules.

WC06 10:00 – 10:15 3D PRINTED ANTENNA DESIGNS FOR FOURIER TRANSFORM MICROWAVE SPECTROSCOPY WC03 9:06 – 9:21 JOHN K KOPP, Chemical Engineering, Kettering University, Flint, MI, USA; NICK KNOWLES, Chemistry, HORNLESS CHIRPED PULSE FOURIER TRANSFORM MICROWAVE SPECTROMETER Kettering University, Flint, MI, USA; CHRIS DEWBERRY, Department of Chemistry & Biochemistry, Kettering EMILY DUNKEL, CHRIS DEWBERRY, Department of Chemistry & Biochemistry, Kettering University, Flint, University, Flint, MI, USA. MI, USA. Traditionally antennas for Fourier transform microwave spectrometers have been the classic ”L” shaped antennas. Here Broadband horn antennas have been used for Fourier transform microwave spectroscopy for a little over a decade. In this we will discuss how 3D printing can be used to quickly prototype various designs and sizes for antennas and antenna arrays report, we will show a more cost effective alternative in describing the reduced cost tandem cavity - chirped pulse FTMW to give insight on optimal antenna for FTMW. This work largely focuses on the receiving antenna and fractal designs. spectrometer being constructed in Flint, Michigan. Intermission 142 143

WC07 10:54 – 11:09 WC09 11:30 – 11:45 A 180 GHZ PULSED TRANSMITTER AND HETERODYNE RECEIVER 28 NM CMOS CHIPSET FOR MOLECULAR ROTATIONAL SPECTROSCOPY: A LABORATORY FOR UNDERGRADUATE PHYSICAL CHEMISTRY SENSING NICOLE MOON, AMANDA JO DUERDEN, G. S. GRUBBS II, Department of Chemistry, Missouri University DEACON J NEMCHICK, BRIAN DROUIN, ADRIAN TANG, MARIA ALONSO, YANGHYO KIM, Jet of Science and Technology, Rolla, MO, USA. Propulsion Laboratory, California Institute of Technology, Pasadena, CA, USA; M.-C. FRANK CHANG, Elec- trical Engineering, University of California - Los Angeles, Los Angeles, CA, USA. While rotational spectroscopy has become a more prominent field within the past few decades, few laboratory exercises exist that introduce The size, weight, and power requirements of emerging millimeter-wave transmitter and receiver integrated circuit ele- students at the undergraduate level to the concepts and instrumentation used ments make them ideally suited for use in high-resolution in situ gas sensors. Previous work at the Jet Propulsion Laboratory within the field. Here, a physical chemistry laboratory involving the analy- has demonstrated a tunable 90-105 GHz transmitter fabricated in 65 nm complementary metal-oxide semiconductor (CMOS) sis of benzonitrile with a Balle-Flygare type, Fourier Transform microwave process having phase noise and output power characteristics suitable for making sub-doppler measurements when deployed spectrometer is introduced as one such exercise. The analysis of benzoni- as the source in a traditional frequency modulated absorption spectrometer.a When paired with a heterodyne receiver of com- trile is ideally suited for an undergraduate physical chemistry laboratory plementary bandwidth and cavity end mirror outfitted with embedded coplanar waveguides a miniaturized cavity enhanced because it is easily carried out within one lab period and involves a compre- pulsed Fourier transform spectrometer can be realized where all source and detection electronics are housed on a single 100 hensive introduction into the world of rotational spectroscopy. Within this cm2 printed circuit board. b laboratory, students have the opportunity to make Gaussian calculations, This talk will highlight ongoing work to expand our current capabilities in order to target more strategic molecular accrue spectra on a research grade FTMW, and perform effective Hamil- 31 3 ← 22 0 ← 2 transitions, such as the , , (JKa ,Kc JKa,Kc )H O line at 183.310 GHz, with a new Tx/Rx chipset. Unlike the tonian fits inclusive of nuclear electric quadrupole coupling using analysis previous generation these integrated circuit elements, now fabricated with 28 nm CMOS techniques, deploy a 90 GHz phase- software commonly available to the spectroscopic community. The design, lock loop the output of which is either frequency doubled, pulse modulated, then amplified (as in Tx) or frequency doubled implementation, and students’ response to this laboratory will be discussed. for use in pumping a down-conversion mixer (as in Rx). Preliminary results will be presented along with a discussion on how the higher frequency radiation generated from these devices can be coupled into (and out of) an optical cavity to allow for exploitation of sensitive pulsed emission schemes. WC10 11:48 – 12:03 TWO-DIMENSIONAL LASER INDUCED FLUORESCENCE SPECTROSCOPY OF MGOMG aD. J. Nemchick et al., “Sub-Doppler spectroscopy with a CMOS transmitter,” IEEE Trans. THz Sci. Technol., vol. 8, no. 1, pp. 121-126, 2018. bD. J. Nemchick et al., A 90-102 GHz CMOS based pulsed Fourier transform spectrometer: New approaches for in situ chemical detection and millimeter-wave cavity-based molecular spectroscopy Rev. Sci. Inst., vol. 89, pp. 073109:1-12, 2018 SEAN MICHAEL BRESLER, JOEL R SCHMITZ, MICHAEL HEAVEN, Department of Chemistry, Emory University, Atlanta, GA, USA.

Two-dimensional laser induced fluorescence spectroscopy is typically implemented using a monochromator equipped with an array detector to record segments of the dispersed fluorescence spectra for each laser excitation wavelength. When pulsed laser excitation is used the capabilities of this system for disentangling complex spectra can be further enhanced by time-gating the array detector. In the present work we are using an Intensified Charge-coupled Device (iCCD) that provides nanosecond time resolution and detection sensitivities that are comparable to photomultiplier tubes. We describe the marriage of a refurbished monochromator, an iCCD, and an Arduino microcontroller to collect temporally and spatially resolved emission spectra of transient small molecules. Recent data for the electronic transitions of the hypermetallic oxide MgOMg will be presented.

WC08 11:12 – 11:27 A LOW-BUDGET, RESEARCH GRADE, BALLE-FLYGARE CAVITY FTMW SPECTROMETER IMPLEMENTED FOR THE TEACHING LABORATORY

AMANDA JO DUERDEN, NICOLE MOON, G. S. GRUBBS II, Department of Chemistry, Missouri University of Science and Technology, Rolla, MO, USA.

Recent advancements in microwave technology have greatly reduced the prices of microwave circuit hardware and signal processing (digitization components). Using a combination of purchased (refurbished) and existing hardware, a “new” research-grade FTMW spectrometer has been constructed with minimal investment. This instrument has the capability to include multiple microwave excitations/collections (FIDs) on a single gas pulse. These features are hardware controlled, but can easily be integrated into software routines. Testing has been performed to minimize the necessary circuit components while also maximizing signal fidelity. Operation of the instrument, in- cluding tests with OCS and Benzonitrile, will be discussed. 144 145 WD. Electronic structure, potential energy surfaces Wednesday, June 19, 2019 – 8:30 AM WD03 9:06 – 9:21 FITTING AN ACCURATE AB INITIO POTENTIAL ENERGY SURFACE FOR THE GROUND ELECTRONIC STATE Room: 217 Noyes Laboratory 16 −1 OF H2 O INCLUDING ENERGY LEVELS UP TO 37 000 cm

Chair: Michael Heaven, Emory University, Atlanta, GA, USA EAMON K CONWAY, Atomic and Molecular Physics , Harvard-Smithsonian Center for Astrophysics, Cam- bridge, MA, USA; IOULI E GORDON, Atomic and Molecular Physics, Harvard-Smithsonian Center for Astro- physics, Cambridge, MA, USA; ALEKSANDRA A. KYUBERIS, Microwave Spectroscopy, Institute of Applied Physics, Nizhny Novgorod, Russia; OLEG L. POLYANSKY, Department of Physics and Astronomy, University College London, Gower Street, London WC1E 6BT, United Kingdom; SERGEI N. YURCHENKO, Department of Physics and Astronomy, University College London, Gower Street, London WC1E 6BT, United Kingdom; WD01 8:30 – 8:45 NIKOLAY F. ZOBOV, Microwave Spectroscopy, Institute of Applied Physics, Nizhny Novgorod, Russia. LASER-INDUCED FLUORESCENCE (LIF) OF JET-COOLED THORIUM NITRIDE (ThN) We present our work on a new semi-empirical potential energy surface (PES) for the ground electronic state of the main JOEL R SCHMITZ, MICHAEL HEAVEN, Department of Chemistry, Emory University, Atlanta, GA, USA. water isotopologue that provides accurate energy levels up to 37 000 cm−1. A previous attempt (Polyansky et al. (2018)) to model the highly energetic levels has seen two independent potentials being merged together into one, however, to date, it is Due to their higher melting point and metal ion density compared to their oxide counterparts, actinide nitrides are promis- the only PES available that can provide the necessary wave-functions needed to compute theoretical intensities in the visible ing candidates for nuclear fission sources in nuclear reactors. While thorium mononitride (ThN) is a possible fission source and near UV. The purpose of this work is to quantify the error associated with the underlying PES for visible near UV line in thorium-based reactors, few studies on ThN have been conducted. Previous ThN studies have characterized gas-phase intensities. rovibronic transitions through resonance-enhanced multiphoton ionization (REMPI) and laser-induced fluorescence (LIF) An initial ab initio PES has been fitted to 16 170 aug-cc-pCV6Z DKH2 MR-CI data points with a functional form utilizing spectroscopic methods[1]. These uncalibrated low-resolution survey spectra, however, were mostly unanalyzed. A cali- only 251 parameters. So far, it has been refined to over 3 500 energy levels originating from both MARVEL (Furtenbacher 2 + brated, higher resolution spectrum was recorded for one vibronic band ([20.9]1.5-X Σ ) and spectroscopic constants were et al. (2007)) and experiment which include rotational levels 0, 1, 2, 3, 4 and 5. Approximately 99% of all possible energy 2 + reported for the ground state and the electronically excited state[1]. More recently, a second band ([18.0]1.5-X Σ ) has been levels have been included in the refining process. The RMS deviation for all levels is currently 0.08 cm−1. observed at high-resolution and used to examine the fine and hyperfine structure of ThN(X)[2]. In the present study, ThN It is generally understood that the dipole moment surface (DMS) provides the largest uncertainty to computed intensities, −1 was jet-cooled to approximately 100K and LIF spectra were recorded over the range 20,000-21,300 cm . A tellurium (Te2) however our results indicate that the error associated with the PES is not negligible, even for the fundamental bands where it ◦ cell was heated to 650 C and its absorbance spectrum was used for spectral calibration. Data and analyses of the observed can rise to 1%. That number is some times higher for other bands. This becomes significant in interpreting the atmospheric ground state and excited states of ThN will be presented. spectra where the quality of the modern spectrometers places high demands on the accuracy of reference spectroscopic data. [1] M.C. Heaven, B.J. Barker, I.O. Antonov, J. Phys. Chem. A, 118 (2014) 10867-10881. Through comparisons with the latest available experiments and observations we provide an analysis on the sensitivity of line [2] A. T. Le, S. Nakhate, T. Nguyen, T. C. Steimle, M. C. Heaven, J. Chem. Phys., submitted intensities from the infrared to the near UV.

WD02 8:48 – 9:03 EXPERIMENTAL DETERMINATION OF THE POTENTIAL ENERGY FUNCTION OF THE COPPER DIMER WD04 9:24 – 9:39 GROUND STATE AB INITIO STUDY OF GROUND-STATE CS PHOTODISSOCIATION VIA HIGHLY EXCITED ELECTRONIC STATES

PETER BORNHAUSER, MARTIN BECK, QIANG ZHANG, GREGOR KNOPP, Photonics, Paul Scherrer In- ZHONGXING XU, Department of Chemistry, The University of California, Davis, CA, USA; NAN LUO, De- stitute, Villigen, Switzerland; ROBERTO MARQUARDT, Laboratoire de Chimie Quantique, Institut de Chimie, partment of Chemical Engineering, University of California, Davis, Davis, CA, USA;WILLIAMM.JACK- Universite´ de Strasbourg, 67008 Strasbourg, France; PETER RADI, Photonics, Paul Scherrer Institute, Villigen, SON, CHEUK-YIU NG, Department of Chemistry, The University of California, Davis, CA, USA;STEVEN Switzerland. FEDERMAN, Physics and Astronomy, University of Toledo, Toledo, OH, USA; LEE-PING WANG, KYLE N. CRABTREE, Department of Chemistry, The University of California, Davis, CA, USA. The copper dimer has attracted much interest from both experimentalists and theorists owing to the relatively simple electronic configuration, the closed d shell and the filled σ orbital in its electronic ground state, which makes it a good Wavelength-dependent photodissociation cross sections are key data required by modern astrochemical models to sim- starting point to understand bonding properties of electronically more complex transition metal dimers. In this talk, we ulate the evolution of chemical species in photon-dominated regions. Although photodissociation is considered as the dom- present a spectroscopic study of dicopper aimed at mapping out its electronic ground state potential energy function at high inant destruction pathway for carbon monosulfide (CS) in these enviroments, the photodissociation rate pf CS is essentially precision. The Cu2 molecules are produced in a home-built laser vaporization source and cooled by a near supersonic unknown due to a lack of vacuum ultraviolet (VUV) laboratory measurements and accurate theoretical calculations. Here expansion in a molecular beam environment. Rotationally resolved stimulated emission pumping (SEP) spectra have been 63 63 65 we present a high-level ab initio study of CS photodissociation, including for the first time a detailed investigation of its recorded for both main isotopologues, Cu2 and Cu Cu, by applying non-linear two-color resonant four-waving mixing predissociation via the B 1Σ+ and C 1Σ+ states. Potential energy curves of CS electronic states were calculated at the (TC-RFWM) technique. Double-resonance schemes involving perturbation assisted excitations opened ways to access high- MRCI+Q/aug-cc-pV(5+C)Z level and photodissociation cross sections from the vibrational and electronic ground state were lying vibrational levels of the ground state. The determined energies and inertial rotational constants of v up to 103 are calculated by solving the coupled-channel Schrodinger¨ equation. We found that the C − X (0 − 0) transition followed by analyzed by using a near-dissociation equation taking into account the dominant long-range dispersion term. The applied spin-orbit coupling into several triplet states is responsible for 73% of the overall photodissociation of CS under the standard iteration procedure yields an accurate RKR potential and refined molecular constants up to the dissociation asymptote. We interstellar radiation field (ISRF), giving rise to the main atomic products C (3P )andS(1D). Our new calculations of the report the determined dissociation energy and the vibrational quanta at the upper limit of the bonding. These experimental photodissociation rate are a factor of 2.4 larger than the value currently adopted by the Leiden database, suggesting that this results extend our knowledge of the copper dimer bonding and provide a benchmark for assessing the accuracy of ab initio value may be revised for improving the accuracy of astrochemical models. calculation. 146 147

WD05 9:42 – 9:57 WD07 10:54 – 11:09 EVALUATING VPT2 SCHEMES FOR ACCURATE AUTOMATED THERMOCHEMISTRY AND SPECTROSCOPY ELECTRONIC AND VIBRATIONAL STRUCTURE OF BUCKY BOWL FOR NON-COVALENT SYSTEMS MASAAKI BABA, AYUMI KANAOKA, Division of Chemistry, Graduate School of Science, Kyoto Univer- BRADLEY WELCH, RICHARD DAWES, ERNESTO QUINTAS SANCHEZ,´ Department of Chemistry, Mis- sity, Kyoto, Japan; MASATOSHI MISONO, Applied Physics, Fukuoka University, Fukuoka, Japan; HIDEHIRO souri University of Science and Technology, Rolla, MO, USA; BRANKO RUSCIC, DAVID H. BROSS, Chemical SAKURAI, Division of Applied Chemistry, Graduate School of Engineering, Osaka University, Suita, Japan; Sciences and Engineering Division, Argonne National Laboratory, Argonne, IL, USA. MASASHI TSUGE, Institute of Low Temperature Science, Hokkaido University, Sapporo, JAPAN; PAVITHRAA SUNDARARAJAN, Department of Applied Chemistry, National Chiao Tung University, Hsinchu, Taiwan; High level computational thermochemical protocols take an additive approach to computing the total energy of a molec- YUAN-PERN LEE, Department of Applied Chemistry, National Chiao Tung University, Hsinchu, Taiwan. ular system. For small systems, components related to the electronic structure can be systematically converged using methods such as coupled-cluster theory at the complete basis limit. The vibrational level pattern (and at 0 K the zero-point energy, ZPE) Bucky bowl is the molecule of nonplanar polycyclic aromatic hydrocarbons. We analyzed the vibronic sructure in the S1 yields a relatively large contribution and is thus a possible source of significant error. An inaccurate ZPE leads to poor quanti- ← S0 fluorescence excitation spectra of jet-cooled sumanene and corannulene. The spectrum is congested with a large number ties such as enthalpies of formation and hence interpretations in kinetics and dynamics. As a result an accurate determination of vibronic bands, which are mostly assigned to out-of-plane vibrational modes. The S1 state of corannulene is identified to 1 1 of this one term is critical and the focus of this talk. Accurate anharmonic models such as VPT2 and VCI exist for semi-rigid E2 by the normal mode analysis, which is consistent with the result of SAC-CI calculation. The excitation energy of A2 1 molecules in the gas phase. Non-covalent systems are also of importance in a wide range of areas. The VPT2 model has state was lower than that of the E2 state by the TD-DFT method. The isolated corannulene molecule is considered to be a not been applied as widely to non-covalent systems and questions remain as to its general applicability. Here, a screening of normal pentagon with considerable out-of-plane distortion (C5v). low-cost implementations of VPT2 calculations were performed for a series of vdW systems as large as Benzene-Ar. The We observed the IR spectrum of corannulene in solid para-H2, which also indicates that the moelcule has a structure screening was done with an automated thermochemical protocol. Comparisons are made with full-dimensional variational with five-fold symmetry in the S0 state. We found the IR bands originated from protonated corannulene molecules, which calculations using global potential energy surfaces, and to experimental data where available. are produced by the chemical reaction with a proton.

[1] P. Sundararajan, M. Tsuge, M. Baba, and Y.-P. Lee, ACS Earth Space Chem. 2, 1001 (2018) [2] S. Kunishige, M. Baba, H. Sakurai, et al., J. Chem. Phys. 139, 044313 (2013) Intermission

WD06 10:36 – 10:51 ELECTRON IMPACT EXCITATION OF GAS-PHASE GUANINE MOLECULES

I.I. SHAFRANYOSH, YU.YU. SVYDA, M.I. SUKHOVIYA, M.I. SHAFRANYOSH, Physics, Uzhhorod Na- tional University, Uzhhorod, Ukraine.

The important components of the DNA and RNA macromolecular “architecture” constitute the nucleobases species: WD08 11:12 – 11:27 adenine, guanine, thymine, uracil and cytosine. The natural energetic state of these molecules provides the stability of bonds in HIGH-RESOLUTION LASER SPECTROSCOPY OF THE S1 ← S0 TRANSITION OF FLUORENE AND CARBAZOLE the complementary pairs of the macromolecules, synthesis of proteins and the genetic function of nucleic acids. Listed above functions can be lost or changed due to the low-energy electron interactions with these molecules. Mentioned electrons are SHUNJI KASAHARA, Molecular Photoscience Research Center, Kobe University, Kobe, Japan;SHINJI formed in the biological objects due to the external irradiation. Currently there is a small number of available investigations KURODA, Graduate School of Science, Kobe University, Kobe, Japan; SHOYA UEDA, Undergraduate, Kobe of the excitation processes of molecule of the nitrogenous bases in the gas phase. In the present work, the results of the University, Kobe, Japan. investigations of the luminescence of guanine molecules in gas phase under the influence of the electron beam are presented. ← Note that similar investigations for guanine molecules are not available in the known literature. In the present work, we carried Rotationally-resolved high-resolution fluorescence excitation spectra of the S1 S0 electronic transition of fluorene and carbazole have been observed. Sub-Doppler excitation spectra were measured by crossing a single-mode UV laser beam out the experiments by the optical method, which had been used before [1]. The gas phase of guanine molecules was formed −1 through the heating of the guanine polycrystalline powder in a separate stainless steel container. In the present work, first, perpendicular to a collimated molecular beam. The absolute wavenumber was calibrated with accuracy 0.0002 cm by the luminescence spectra of guanine molecules in gas phase are obtained in the wavelength range of 250–500 nm under the measurement of the Doppler-free saturation spectrum of iodine molecule and fringe pattern of the stabilized etalon. For 00 00 + 1228 −1 influence of electron beams of different energies. 19 molecular bands and lines are clearly manifested in the spectra of guanine fluorene, 7 bands were observed and analyzed from the 0 to 0 cm band, and their molecular constants were 00 00 + 1122 −1 in gas phase. Their maxima are located at the following wavelengths: λλ= 289.2; 304.2; 307.2; 315.9; 326.8; 337; 355.5; determined with high accuracy. For carbazole, 3 bands were observedand analyzed from the 0 to 0 cm band, and a 359.2; 362; 367.1; 386.1; 388.2; 391.6; 395.4; 415.5; 430.5; 434.1; 447.3; 486.1 nm. The quantity and shape of the spectral their molecular constants were also determined. Yi et. al. were reported the lower vibronic bands for both molecules, and 00 + 204 −1 bands indicate that the nature of their origin is connected with the excitation of the electronic states both of the whole molecule their molecular constants are good agreement with the obtained ones except the 0 cm band of fluorene. We found 00 +204 −1 and its ionized or neutral fragments (dissociative excitation, dissociative excitation with ionization). Practically all bands have a typical local energy shift in this 0 cm band, and it was identified as originating from the perturbation between the 00 a complex character and this fact testifies to their superposition nature. It was discovered that guanine can be transformed vibronic levels in the S1 state. The Zeeman effect were also observed up to 1.2 T for the 0 bands to consider the excited state into the adenine molecular ion in case of an inelastic interaction. In other words, the phenomenon of transmutation of the dynamics. nitrogenous base occurs and that fact has exclusively radiobiological significance. Reference 1. Shafranyosh I.I., Sukhoviya aJ. T. Yi, L. Alvarez-Valtierra, and D. W. Pratt, J. Chem. Phys., 124, 244302 (2006). M.I. Inelastic collisions of the uracil molecules with electrons // J.Chem.Phys. 2012, V.137, N.18, pp.184303-9. 148 149 WE. Mini-symposium: High-Harmonic Generation and XUV Spectroscopy WD09 11:30 – 11:45 LIF SPECTROSCOPY OF LINEAR SiOSi Wednesday, June 19, 2019 – 8:30 AM

MASARU FUKUSHIMA, TAKASHI ISHIWATA, Information Sciences, Hiroshima City University, Hiroshima, Room: B102 Chemical and Life Sciences Japan. Chair: Agnieszka Jaron-Becker, University of Colorado, Boulder, USA We have assigned spectral species of a LIF spectrum with 1Π – 1Σ rotational structure to SiOSi with the aid of ab initio quantum chemical calculationsa. Due to the spectrum’s red-shaded structure, the R-branch forms a band head, and an analysis adopting the P -andQ-branches had not been satisfactory. As the ab initio calculations suggest the ground electronic state is 1Σ+ 1 g , we attempted a more precise analysis via combination differences and noted heavy irregularities exclusive to the upper levels of the Q-branch. Considering parities of the rotational levels of the upper Π electronic state, we are investigating this irregularity with the aid of computation.

aM. Fukushima and T. Ishiwata, 73rd ISMS, paper MJ09 (2018). WE01 Journal of Molecular Spectroscopy Review Lecture 8:30 – 9:00 WD10 Post-Deadline Abstract 11:48 – 12:03 SIMULATING STRONG FIELD RESCATTERING USING ATTOSECOND LIGHT THE ELECTRONIC STRUCTURE OF THE PLANARIZED BLATTER RADICAL AND ITS DERIVATIVES. LOUIS DIMAURO, Department of Physics, The Ohio State University, Columbus, OH, USA. ANIKET HANDE, CLOVIS DARRIGAN, Institute of Analytical Sciences and Physical Chemistry for the Envi- ronment and Materials, CNRS/ UNIV PAU0 & PAYS ADOUR/ E2S UPPA, Pau, France; PIOTR KASZYNSKI,´ An atom or molecule interacting with an intense, ultrafast laser pulse is a fundamental problem in modern physics. Department of Chemistry, University of Łod´ z,´ Łod´ z,´ Poland; ANNA CHROSTOWSKA, Institute of Analytical At intensities that are approximately one-tenth an atomic unit of field (50 V/A) the physics is well described by a semi- Sciences and Physical Chemistry for the Environment and Materials, CNRS/ UNIV PAU0 & PAYS ADOUR/ E2S classical 3-step model where an electron tunnel ionizes, driven by the strong-field and then rescatters with its parent core. The UPPA, Pau, France. consequence of this physics has opened the areas of attosecond science and spatial-temporal molecular imaging. However in a strong field experiment, the exponential rate of tunnel ionization fixes the release phase of the electron wave packet (EWP) In recent years, derivatives of the 1,4 dihydrobenzo[e][1,2,4]triazin-4-yl radical (e.g. the Blatter1 radical a) are gaining at the extreme of the laser field. In this talk, we will describe a method that allows for more precise studies of the strong much interest due to their properties, such as exceptional stability, spin Π-delocalization, narrow electrochemical window field process. The approach simulates the 3-step model by replacing the tunneling step with single-photon ionization by an and low excitation energies. For these reasons, a rapidly increasing attention is given to these radicals as structural elements attosecond XUV pulse. A phase-locked intense low-frequency field drives the EWP mimicking steps (2) and (3) but with of advanced materials.b Their design requires, however, a good understanding of the electronic structure of these electro-, little or no ionization. We will present both experimental and theoretical results demonstrating the viability of this approach. photo- and magnetically active molecular components. Recent advances in the chemistry of the 1,4-dihydrobenzo[e][1,2,4]triazin-4-yl demonstrated access to the parent “pla- narized” Blatter radical, in which more effective spin delocalization onto the Ph ring at the N(1) position is observed.c In order to better understand the impact of electronic delocalization on properties of the radicals, a series of derivatives has been prepared and investigated by computational and spectroscopy methods. Herein we present determination of the electronic structure of a series of substituted planar radical using UV photoelec- tron spectroscopy (UV-PES), EPR, and UV-vis spectroscopy.

aBlatter, H. M.; Lukaszewski, H. A New Stable Free Radical. Tetrahedron Lett. 1968, 9, 2701–2705. WE02 9:06 – 9:21 bJasinski,´ M.; Szczytko, J.; Pociecha, D.; Monobe, H.; Kaszynski,´ P. ”Substituent-dependent magnetic behavior of discotic benzo[e][1,2,4]triazinyls”, J. Am. Chem. Soc. 2016, 138, 9421-9424. Kapusci´ nski,´ S.; Gardias, A.; Pociecha, D.; Jasinski,´ M.; Szczytko, J.; Kaszynski,´ P. ”Paramagnetic bent-core mesogens derived from the 1,4- CHARACTERIZATION OF PHOTOINDUCED VALENCE TAUTOMERISM IN A COBALT DIOXOLENE COMPLEX dihydrobenzo[e][1,2,4]triazin-4-yl”, J. Mater. Chem. C, 2018, 6, 3079–3088. BY FEMTOSECOND M-EDGE SPECTROSCOPY cKaszynski,´ P.; Constantinides, C. P.; Young, V. G. The Planar Blatter Radical: Structural Chemistry of 1,4-Dihydrobenzo[e][1,2,4]triazin-4-yls. Angew. Chem. 2016, 128, 11315–11318. RYAN T ASH, Chemistry, University of Illinois at Urbana-Champaign, Urbana, IL, USA; KAILI ZHANG, JOSH VURA-WEIS, Department of Chemistry, University of Illinois at Urbana-Champaign, Urbana, IL, USA.

Cobalt dioxolene complexes undergoing photoinduced valence tautomerism (VT) are potential candidates for molecular electronic devices. Thermal or photoinduced electron transfer between a dioxolene ligand and the metal center reversibly switch the complex between a paramagnetic or diamagnetic species. A low-spin CoII intermediate is believed to be involved in the photogeneration of the paramagnetic state from the diamagnetic state, but has not been spectroscopically observed yet. Our group has developed a tabletop M-edge XANES spectrometer which generates femtosecond extreme ultraviolet pulses via high-harmonic generation (HHG). M-edge spectroscopy has been shown to be sensitive to changes in oxidation state, spin state and/or ligand field changes at metal centers, and the spectra can be predicted using ligand field multiplet theory. In this work, we will present temperature dependent and time-resolved spectra of a cobalt dioxolene VT compound and highlight the ultrafast electron transfer and spin state changes. The theoretical tools developed to predict and interpret the M-edge spectra of metal-centered excited states will also be discussed. This work demonstrates that HHG-based XUV absorption spectroscopy is an accessible alternative to synchrotron-based X-ray absorption spectroscopy for elucidating the electronic structure and photoinduced dynamics of transition metal complexes. 150 151

WE03 9:24 – 9:39 WE05 10:36 – 10:51 DETERMINING THE PRESENCE OF SPIN DYNAMICS IN COBALT FERRITE THIN FILMS USING XUV-RA SPEC- CALCULATIONS OF MICROSCOPIC AND MACROSCOPIC PROPERTIES OF HIGH-HARMONIC GENERATION TROSCOPY FROM MOLECULAR IONS

STEPHEN LONDO, SOMNATH BISWAS, JAKUB HUSEK, ROBERT BAKER, Department of Chemistry and TJOYCE, AGNIESZKA JARON-BECKER, JILA and Department of Physics, University of Colorado, Boulder, Biochemistry, The Ohio State University, Columbus, OH, USA. CO, USA.

Spin crossover (SCO) metal-organic complexes have seen recent advances for their applicability in spintronic devices by High-harmonics generated in molecules can contain information about exhibiting bidirectional stability between high-spin (HS) and low-spin (LS) states upon application of external stimuli. How- electronic structure and time-dependent dynamics induced by the driving laser. ever, adsorbing these molecular complexes onto surfaces can dramatically change their SCO characteristics so alternative In molecular ions, it was recently predicted that the usual odd harmonics can 102 materials are being explored. Cobalt ferrite (CFO, CoFe2O4) thin films are presently studied for their ability to induce mag- be accompanied by sidebands at non-integer multiples of the fundamental fre- netism but may exhibit SCO the same way Fe/Co Prussian Blue molecular analogs SCO after photoexcitation. To investigate quency, analogous to the appearance of Mollow triplets in quantum optics [see 100 the potential SCO dynamics of CFO, we employ reflection-absorption extreme ultraviolet (XUV-RA) spectroscopy which is figure]. These sidebands result from competition between two nonperturbative element and oxidation state specific and sensitive to changes in the local geometry and spin state. Photoexciting CFO initiates processes, Rabi oscillation and high-harmonic generation, and therefore offer 10−2 an electron transfer from Co2+ to Fe3+, reducing iron and oxidizing cobalt. By comparing time-averaged experimental spec- additional insight into the dynamics of the molecule in a strong laser field. 3+ 10−4

tra to charge-transfer multiplet simulations, we find excellent agreement with LS Co CFO indicating a SCO from native HS While the Mollow sideband effect shows up in theoretical calculations of Harmonic Yield (arb. units) 2+ Co after photoexcitation. Kinetic analysis using a two-state sequential model produces a SCO time constant of 245 ± 30 single-molecule harmonic generation, in principle the macroscopic response 10−6 fs and the initial and final state solutions agree well with simulated HS and LS Co3+ CFO spectra respectively. The driving must also be calculated to obtain a complete description. We evaluate the 1 3 5 7 9 11 13 15 mechanism for SCO is small hole polaron formation evident by changes in the oxygen L1-edge signature. Hole polarons macroscopic harmonic spectrum by combining many single-molecule calcula- Harmonic Number compress the oxygen lattice around photoexcited Co3+ increasing the crystal field splitting of hybrid Co3+ 3d orbitals and tions at different intensities, obtained from time-dependent density functional + enabling the initially blocked oxygen 2s → 2p transition. These results demonstrate the ability of XUV-RA to capture the theory calculations of N2 , and also from a 1D model potential. Our results Figure 1: Calculated macrosopic high- femtosecond spin dynamics of metal oxide materials and provides insight into the SCO characteristics of CFO for use in suggest that the Mollow sidebands are approximately the same intensity as the harmonic signal in the forward direction. spintronic devices. main harmonics, and also they are radiated at wider angles, meaning they could Mollow sidebands appear spaced by half the be isolated more easily in an experiment. Rabi frequency to either side of the main This work was supported by NSF JILA Physics Frontier Center (Grant No. harmonics. PHY 1734006)

WE04 9:42 – 9:57

OBSERVATION OF TRANSIENT HIGH-VALENT STATES IN THE WATER OXIDATION CATALYST CoIII4O4 WE06 10:54 – 11:09 CUBANE VIA EXTREME ULTRAVIOLET SPECTROSCOPY APPLYING XUV SPECTROSCOPY TO OBSERVE SPIN-ORBIT STATE DEPENDENCE ON STRONG-FIELD IONIZA- YUSEF A. SHARI’ATI, Chemistry, University of Illinois at Urbana-Champaign, Urbana, IL, USA;JOSH TION VURA-WEIS, Department of Chemistry, University of Illinois at Urbana-Champaign, Urbana, IL, USA. SCOTT G SAYRES, School of Molecular Sciences, Arizona State University, Tempe, AZ, USA. The tetranuclear metal-oxo complex [CoIII4O4](OAc)4(py)4 is a homogeneous wa- ter oxidation catalyst and structural mimic of the oxygen evolving complex in photosyn- Strong-field ionization (SFI) has become a major workhorse of modern ultrafast spectroscopy and appears at the very thetic organisms. The catalytic cycle involves a highly-oxidized intermediate the nature heart of the high-harmonic generation process that is responsible for the production of extreme ultraviolet (XUV) laser pulses. of which is controversial: leading formulations argue for either [CoIV 2CoIII2O4]or When SFI is synchronized to another laser pulse through the pump-probe technique, this attosecond process can be used to [CoV CoIII3O4]. arrest the intermediates of ultrafast photochemical reactions as well as explore the electronic structure of both atoms and We report the sensitization of the [CoIII4O4] cubane with a perylene bisimide dye molecules. In this talk, I will highlight our recent results where XUV transient absorption spectroscopy is used to measure thus enabling photoinduced electron transfer upon green light illumination and effecting the angular distributions of singly and doubly tunnel-ionized xenon atomic states via 4d core to 5p valence shell transitions a transient oxidation of the cobalt center(s). The resultant high-valent states and their between 55 and 60 eV. Orbital alignment measurements and theory are used to examine the role of electron correlation during dynamics are probed by ultrafast transient absorption and extreme ultraviolet (XUV) spec- atomic strong-field double ionization. The experimental MJ alignment distributions are compared to results of a rate-equation troscopies. XUV spectroscopy, by dint of its oxidation-state specificity, has the potential model based on sequential ionization and are now applied to account for the alignment prepared by tunneling ionization. The to reveal the true distribution of holes among cobalt centers within the oxidized cluster. incredible energy and time resolution afforded through XUV spectroscopy is utilized to reveal entirely new information about the strong-field ionization mechanism, including new details about contrasting ionization timescales and orbital alignment of different spin-orbit states. The electron dynamics that operate during tunneling ionization reveal details about electron correlation that are fundamentally important for understanding light-matter interaction.

Intermission 152 153 WF. Ions WE07 11:12 – 11:27 Wednesday, June 19, 2019 – 8:30 AM ATTOSECOND STREAKING TIME DELAYS: FINITE-RANGE INTERPRETATION AND APPLICATIONS Room: 2079 Natural History ANDREAS BECKER, JILA and Department of Physics, University of Colorado, Boulder, CO, USA;CORY GOLDSMITH, JILA and Department of Chemistry, University of Colorado, Boulder, CO, USA;TJOYCE,AG- Chair: Gary E. Douberly, The University of Georgia, Athens, GA, USA NIESZKA JARON-BECKER, JILA and Department of Physics, University of Colorado, Boulder, CO, USA.

We present theoretical studies of the attosecond streaking time delay concept in photoionization via the investigation of the electron dynamics in the streaking field after the transition of the photoelectron into the continuum upon absorption of an extreme ultraviolet photon. Based on the results, a so-called finite range interpretation is introduced, that highlights that the delay is accumulated until the streaking pulse ends and, hence, over a finite range of the potential of the parent ion. We then summarize a few applications which provide insights into different aspects of the streaking time delay concept in photoionization, including the relation to the Wigner-Smith time delay, the role of the attochirp and the extension to two- WF01 8:30 – 8:45 + photon processes. HIGHLY-ACCURATE EXPERIMENTALLY DETERMINED ENERGY LEVELS OF H3 The work has been supported by DOE-BES (Award No. DE-SC0001771). CHARLES R. MARKUS, Department of Chemistry, University of Illinois at Urbana-Champaign, Urbana, IL, USA; BENJAMIN J. McCALL, Departments of Chemistry and Astronomy, University of Illinois at Urbana- WE08 11:30 – 11:45 Champaign, Urbana, IL, USA. GENERATION AND STUDY OF FEW-FEMTOSECOND VIBRATIONAL WAVE-PACKETS VIA STRONG-FIELD ION- + IZATION H3 is the simplest polyatomic molecule, and its rovibrational energy levels provide valuable benchmarks for ab initio + theorists. Calculations of the H3 potential energy surface which take into account effects beyond the Born-Oppenheimer LAUREN F HEALD, School of Molecular Sciences and Biodesign Center for Applied Structural Discovery, approximation can predict rovibrational transitions from low lying states with an accuracy of 0.001 cm−1,a and agreement Arizona State University, Tempe, AZ, USA; SCOTT G SAYRES, School of Molecular Sciences, Arizona State is on the order of 0.01–0.1 cm−1 for transitions from higher levels. As the accuracy of theoretical methods begins to rival University, Tempe, AZ, USA. experimental uncertainties, new measurements are needed to benchmark future ab initio calculations. + In order to provide accurate experimentally determined energy levels, a survey of rovibrational transitions of H3 has Strong-field ionization (SFI) using ultrashort, high-intensity laser pulses presents a unique opportunity for studying dy- been collected using the sub-Doppler technique Noise-Immune Cavity-Enhanced Optical Heterodyne Velocity Modulation namics of molecular systems given its capability to generate coherent vibrational and electronic motion. Furthermore, the Spectroscopy (NICE-OHVMS).b In total, we have measured 56 transitions in the ν2 ← 0 fundamental band,cd 17 transitions 2 2 very interaction that drives the tunneling ionization is at the root of high harmonic generation of extreme ultraviolet light in the 2ν2 ← ν2 hot band, and 7 transitions in the 2ν2 ← 0 overtone band with approximately 4 MHz uncertainty. For most (XUV). Our homebuilt XUV spectrometer is uniquely suited to utilize SFI to study coherent, vibrational wave-packets of transitions, this was an improvement by a factor of 40 or more. Combination differences were used to calculate ground state small molecules in the gas phase given its ability to observe transitions from localized core shells to delocalized valence rotational levels relative to the lowest ortho and para states. A fit of the ground vibrational state to an effective Hamiltonian shells to glean information about their larger molecular systems (e.g. oxidation state, spin state, magnetic quantum number, was used to determine energy levels relative to the forbidden (0,0) rotational state. Overall, 18 absolute energy levels were and local bonding environment). Its temporal resolution provides the capability to observe electronic motion and vibrational determined with uncertainties of approximately 0.0003 cm−1 (10 MHz). In addition, frequencies of forbidden rotational coherences that occur on the few-femtosecond time period. This presentation will focus on the techniques for generating transitions were predicted, including a possible astrophysical maser.e few-cycle XUV pulses and our preliminary computational and experimental results on the dynamics and mechanisms behind a the SFI of simple gas phase systems of fundamental importance for understanding light-matter interactions. L. G. Diniz, J. R. Mohallem, A. Alijah, M. Pavanello, L. Adamowicz, O. L. Polyansky, and J. Tennyson, Phys. Rev. A, 88, 032406 (2013). bB. M. Siller, M. W. Porambo, A. A. Mills, and B. J. McCall, Opt. Express, 19,24822–7 (2011). cJ. N. Hodges, A. J. Perry, P. A. Jenkins II, B. M. Siller, and B. J. McCall, J. Phys. Chem., 139, 164201, (2013). dA. J. Perry, J. N. Hodges, C. R. Markus, G. S. Kocheril, and B. J. McCall, J. Mol. Spectrosc., 317,71–73, (2015). eJ. H. Black, Faraday Discussions, 109, 257–266 (1998).

WF02 8:48 – 9:03 PURE ROTATIONAL SPECTRUM OF CN+

SVEN THORWIRTH, PHILLIP SCHREIER, THOMAS SALOMON, STEPHAN SCHLEMMER, OSKAR AS- VANY, I. Physikalisches Institut, Universitat¨ zu Koln,¨ Koln,¨ Germany.

The pure rotational spectrum of the elusive CN+ cation has been observed for the first time using the cryogenic ion trap apparatus Coltrap by applying an action spectroscopy scheme. For the 12C14N+ species, the three lowest rotational transitions have been observed each of which exhibits hyperfine structure from the presence of the 14N nucleus. The rare 12C15N+ isotopolog has been studied up to the J =4− 3 transition. The observations conclusively confirm CN+ to occupy a 1Σ+ electronic ground state. Given the ubiquity of the CN radical in space, CN+ is an appealing candidate for future radio astronomical searches. 154 155

WF03 9:06 – 9:21 WF05 9:42 – 9:57 − AUTODETACHMENT OF CH2CN VIEWED WITH HIGH RESOLUTION PHOTOELECTRON IMAGING HINDERING AN ION-NEUTRAL REACTION USING VIBRATIONAL EXCITATION: THE ν7 ROVIBRATIONAL + BAND OF c-C3H2 BENJAMIN A LAWS, STEPHEN T GIBSON, Research School of Physics and Engineering, Australian Na- tional University, Canberra, ACT, Australia; RICHARD MABBS, Department of Chemistry, Washington Uni- CHARLES R. MARKUS, Department of Chemistry, University of Illinois at Urbana-Champaign, Urbana, IL, versity, St. Louis, MO, USA. USA; OSKAR ASVANY, THOMAS SALOMON, PHILIPP C SCHMID, SHREYAK BANHATTI, I. Physikalis- ches Institut, University of Cologne, Cologne, Germany; FILIPPO LIPPARINI, Dipartimento di Chimica e Chim- − Previous studies of the cyanomethyl radical CH2CN have ob- ica Industriale, Universita` di Pisa, Pisa, Italy;JURGEN¨ GAUSS, Institut fur¨ Physikalische Chemie, Universitat¨ served sharp resonances in the photoelectron spectrum of the anion, Mainz, Mainz, Germany; SANDRA BRUNKEN,¨ FELIX Laboratory, Radboud University, Nijmegen, The Nether- that occur due to the existence of a dipole bound state (DBS).ab At lands; STEPHAN SCHLEMMER, I. Physikalisches Institut, University of Cologne, Cologne, Germany. 728.2 nm specific detachment wavelengths, the anion may be excited to the DBS, 726.6 nm −9 3 −1 which subsequently autodetaches. Autodetachment transitions may be 726.2 nm Ion-neutral reactions often occur rapidly at Langevin rate constants of ∼ 10 cm s , even at low temperatures, which 721.2 nm + + readily identified in the anion photoelectron spectrum by both their is why they are able to drive the chemistry of interstellar space. The reaction C3H2 + H2 → C3H3 + H does not follow this −13 3 −1 a + sensitivity to laser wavelength, and the differing relationship between trend, and has been known to occur at a much slower rate of ∼ 2 × 10 cm s . It was recently observed that when C3H2 photon and electron energy. ions were resonantly excited by mid-IR light in a multipole ion trap held at 8 K, they were less likely to react with H2 to − + This study investigates CH2CN using high-resolution photoelec- form C3H3 . Here, possible mechanisms behind this inhibited reaction process are discussed. Additionally, this effect can be tron imaging. Spectra were recorded at a range of wavelengths from Intensitry (arb. u.) utilized as a new form of action spectroscopy by counting the number of formed product ions as a function of the excitation 355 − 780 nm, with resonances observed at hv = 662, 722, 725, and wavelength, which was used here to measure 91 rovibrational transitions in the ν7 asymmetric C-H stretch band of the cyclic + 767 nm. These measurements resolve the K-rotational structure of the C3H2 isomer. The new frequencies were used to determine accurate molecular constants that are compared to high-level ab molecule, allowing for the exact rotational transitions involved in the initio calculations. 12200 12400 12600 12800 13000 13200 13400 13600 13800 autodetachment to be identified. The spectra are further complicated Binding Energy (cm−1) aI. Savic´ and D. Gerlich, Phys. Chem. Chem. Phys., 7, 1026–1035, (2005). 2 by the presence of vibronic coupling between the neutral ground B1 2 and excited A1 states, which may be identified from changes in the anisotropy of the electron distribution.

aM. L. Weichman, J. B. Kim, and D. M. Neumark, J. Chem. Phys. 140, 104305 (2014) bJ. Lyle, O. Wedig, S. Gulania, A. Krylov, and R. Mabbs, J. Chem. Phys. 147, 234309, (2017) Research supported by the Australian Research Council Discovery Project Grant DP160102585. Intermission

WF06 10:36 – 10:51 INFRARED PHOTODISSOCIATION SPECTROSCOPY AND MULTIREFERENCE ANHARMONIC VIBRATIONAL + STUDY OF THE HO4 MOLECULAR CATION

PETER R. FRANKE, MICHAEL A DUNCAN, GARY E. DOUBERLY, Department of Chemistry, University of WF04 9:24 – 9:39 Georgia, Athens, GA, USA. + +a + a + SPECTROSCOPIC STUDIES OF PROTONATED AMINES: CH3NH3 AND C2H5NH3 HO4 has been proposed as an astrochemical sink of oxygen but has never been observed. Molecular cations of HO4 + and DO4 are produced in a supersonic expansion. They are mass-selected, and their infrared photodissociation spectra are SVEN THORWIRTH, PHILIPP C SCHMID, MATTHIAS TOPFER,¨ I. Physikalisches Institut, Universitat¨ zu measured with the aid of argon-tagging. Previous theoretical studies have modeled these systems as proton-bound dimers Koln,¨ Koln,¨ Germany; SANDRA BRUNKEN,¨ FELIX Laboratory, Radboud University, Nijmegen, The Nether- of molecular oxygen.b Several conformers were located on the quintet, triplet, and singlet surfaces, differing in energy by, lands; OSKAR ASVANY, STEPHAN SCHLEMMER, I. Physikalisches Institut, Universitat¨ zu Koln,¨ Koln,¨ Ger- at most, a few thousand wavenumbers; the singlet and triplet conformers have pronounced multiconfigurational character. + many. Our HO4 is formed in a relatively hot environment, and similar experiments have been shown capable of producing multiple c + + + conformers in low-lying electronic states. None of the predicted HO4 isomers can be ruled out aprioribased on energetic Mid-infrared spectra of protonated methylamine, CH3NH3 , and ethylamine, C2H5NH3 , have been recorded using the arguments. We interpret our spectra with second-order vibrational perturbation theory with resonances (VPT2+K) using FELion ion trap connected to the Free Electron Laser for Infrared eXperiments (FELIX; Radboud University, Nijmegen, The quartic force fields based on an economical combination of single- and multi-reference theories. The VPT2+K simulations Netherlands) employing infrared photodissociation of the corresponding neon-clusters. In addition, the pure rotational spec- + include the effect of electrical anharmonicity; this is particularly important for transitions involving the shared-proton stretch. trum of CH3NH3 has been observed for the first time. Rotational transitions were observed in the frequency region between Previously unidentified chain structures (H-O-O-O-O) that exist on the singlet and triplet surfaces likely represent the global 80 and 240 GHz in the Coltrap apparatus using the method of state-selective He-attachment. In contrast to methylamine which + minima. features a complex CH3-internal-rotation/NH2-inversion spectrum, its protonated variant CH3NH3 exhibits the spectrum of a a simple symmetric rotor in its ground vibrational state. Xavier, G. D.; Bernal-Uruchurtu, M. I.; Hernandez-Lamoneda, R., J. Chem. Phys. 2014, 141, 5, 081101. bXavier, F. G. D.; Hernandez-Lamoneda, R., PCCP 2015, 17, 16023-16032. cWagner, J. P.; McDonald, D. C.; Duncan, M. A., Angewandte Chemie-International Edition 2018, 57, 5081-5085. aThis contribution is dedicated to the memory of Li-Hong Xu. 156 157

WF07 10:54 – 11:09 WF10 11:48 – 12:03 − AUTODETACHMENT AND VIBRONIC COUPLED PHOTODETACHMENT TRANSITIONS OF C2H3O SOLVATOCHROMIC BEHAVIOR OF THE ANIONIC BIOCHROMOPHORE BILIVERDIN INVESTIGATED USING A CRYOGENIC ION TRAP STEPHEN T GIBSON,BENJAMINALAWS,Research School of Physics and Engineering, Australian Na- tional University, Canberra, ACT, Australia. WYATT ZAGOREC-MARKS, JILA and the Department of Chemistry and Biochemistry, University of Colorado-Boulder, Boulder, CO, USA; LEAH G DODSON, JILA and NIST, University of Colorado, Boulder, CO, − The photoelectron spectrum of the vinoxy anion C2H3O is USA; J. MATHIAS WEBER, JILA and the Department of Chemistry and Biochemistry, University of Colorado- studied using velocity-imaging, with the angular distributions pro- Boulder, Boulder, CO, USA. 1 X̃2A Ã2A 1.0 viding electronic-state and vibrational-mode specific characteriza- C H O tion. A 355 nm photoelectron spectrum, together with anisotropy 2 3 Fluorescent proteins can incorporate a wide variety of chromophores which all lead to different absorption and emission parameters determined for some of the stronger transitions is show β characteristics. In the condensed phase, interactions of chromophores with their chemical environment (e.g., solvents, sur- in the figure. Photodetachment at longer wavelengths have also 0.5 rounding protein) change their photophysical properties. By examining these chromophores as mass-selected ions in vacuo, been measured. we are able to study their intrinsic photophysical properties without influence from such environments. Here we report elec- The spectroscopic analysis builds on a previous SEVIa study, tronic and infrared spectra of cryogenically prepared biliverdin anions. We interpret our experimental spectra through analysis and a CRDSb work. Forbidden asymmetric vibrational modes 0 0.0 of time-dependent density functional theory calculations. may gain intensity through vibronic coupling between the neutral intensity (arb. units)

ground state and an excited state, of the correct symmetry, and anisotropy parameter ˜ have an anomalous anisotropy parameter. The positive X tran- 355 nm 2 1 sition is 90111. In addition, the vinoxy anion has dipole-bound anisotropy −0.8 excited electronic states, that produce very narrow transitions. For 14000 16000 18000 20000 22000 24000 − C2H3O there is evidence of autodetachment from dipole-bound electron binding energy (cm−1) states of the anion, and vibronic coupling of the neutral ground state.

aSlow-Electron-Velocity-map-Imaging: Yacovitch et al. JChemPhys130 244309 (2009) doi:10.1063/1.3157208 bCavity-Ring-Down-Spectroscopy: Thomas et al. JChemPhys132 114302 (2010) doi:10.1063/1.3352976 Research supported by the Australian Research Council Discovery Project Grant DP160102585.

WF08 11:12 – 11:27 VELOCITY MAP IMAGING OF DISSOCIATIVE CHARGE TRANSFER IN TRANSITION METAL ION - MOLECULE COMPLEXES

BRANDON M. RITTGERS, DANIEL LEICHT, MICHAEL A DUNCAN, Department of Chemistry, University of Georgia, Athens, GA, USA.

Transition metal ion-molecule complexes (e.g., M+(benzene), M+(furan), M+(methanol), etc. where M = Zn, Ag, Au) are generated in the gas phase by laser vaporization and are detected using a time-of-flight mass spectrometer. The ionization potentials of the metals are typically lower than those of many molecules, leading to the charge being localized on the metal in a cation-molecule complex. Laser excitation of the ion-molecule complexes leads to a charge transfer dissociation channel producing the molecular ion fragment. If the excitation wavelength is sufficiently high, excess kinetic energy release above the dissociation threshold can be detected using velocity map imaging. This energy release can then be used to calculate an upper bound on the metal ion-molecule bond energy.

WF09 11:30 – 11:45 THRESHOLD IONIZATION SPECTROSCOPY AND SPIN-ORBIT COUPLING OF CeC3H4 and CeC3H6 FORMED in Ce + PROPENE REACTION

YUCHEN ZHANG, WENJIN CAO, DONG-SHENG YANG, Department of Chemistry, University of Kentucky, Lexington, KY, USA.

CeC3H4 and CeC3H6 are observed in the reaction of Ce with propene in molecular beams and characterized by mass- analyzed threshold ionization (MATI) spectroscopy and relativistic quantum calculations. The MATI spectrum of each species displays two band systems, each consisting of vibronic progressions from Ce-C stretching and ligand bending excitations in −1 the ionic states. The adiabatic ionization energies of CeC3H4 and CeC3H6 are 41035 (5) and 41868 (5) cm , respectively. −1 −1 The two band systems are separated by 125 cm for CeC3H4 and 60 cm for CeC3H6. By comparing the splittings from the spectra with the relativistic calculations at the level of multiconfiguration quasi-degenerate second-order perturbation theory, we assign the two band systems to transitions from two spin-orbit levels of the neutral molecules. 158 159

WG. Mini-symposium: Astrochemistry and Astrobiology in the age of ALMA WG02 2:21 – 2:36 DETECTION OF CCCH+ TOWARD W49N: ELUCIDATING THE MOLECULAR COMPLEXITY OF THE DIFFUSE Wednesday, June 19, 2019 – 1:45 PM INTERSTELLAR GAS HARSHAL GUPTA, Division of Astronomical Sciences, National Science Foundation, Alexandria, VA, USA; Room: 116 Roger Adams Lab KELVIN LEE, Radio and Geoastronomy Division, Harvard-Smithsonian Center for Astrophysics, Cambridge, MA, USA; MICHAEL C McCARTHY, Atomic and Molecular Physics, Harvard-Smithsonian Center for Astro- physics, Cambridge, MA, USA.

Chair: Eric R. Willis, The University of Virginia, Charlottesville, VA, USA The simple hydrocarbons CCH, CCCH,c-C3H, H2CCC, and c-C3H2 are common in the interstellar gas and are thought to be important in the production of larger molecules, yet their abundances are poorly understood. Observations of the carbon chain ion CCCH+, a key intermediate in the chemistry of these species, have begun to shed some light on their abundances: (i) maps of CCCH+ in the Horsehead nebula photodissociation region (PDR) suggest that besides ion-molecule chemistry, the fragmentation of large molecules or very small interstellar grains contributes to the production of small hydrocarbons;a and (ii) there is important but limited evidence that the CCCH+ abundance is uniform in diffuse clouds in the Galactic disk, and is remarkably similar to CCCH+ abundances inferred in PDRs.b Furthermore, there is clear evidence for a very large + c + molecule—the fullerene ion C60—in the diffuse gas, so studies of CCCH and similar ions in diffuse clouds should allow robust constraints on chemistry over a very large scale in molecular size. Using the 100-m Green Bank Telescope, we recently detected the two lowest rotational transitions of CCCH+ along with transitions of several related hydrocarbons in absorption from diffuse clouds toward the luminous H II region W49N. Our observations demonstrate that absorption spectroscopy is a highly sensitive means to detect trace polyatomic species such as CCCH+, owing to the large pathlengths through the Spiral Arms and the availability of bright centimeter continuum sources. We will discuss our results toward W49N within the context of elucidating the abundances of small hydrocarbons in diffuse clouds. We will also discuss the prospects of detecting CCCH+ toward several other Galactic continuum regions, and detecting larger polyatomic molecules in diffuse clouds through dedicated spectral line surveys. WG01 INVITED TALK 1:45 – 2:15 aGuzman,´ V., Pety, J., Goicoechea, J. R., et al. 2015, ApJL, 800, L33 ASTROCHEMISTRY OF STAR FORMING REGIONS: FROM SINGLE DISH TO INTERFEROMETRIC OBSERVA- bGerin, M., Liszt, H., Neufeld, D., et al. 2019, A&A, 622, A26; and references therein. TIONS cMaier, J. P. & Campbell, E. K. 2016, Phil. Trans. R. Soc. A, 374, (issue 2076), 1

CHARLOTTE VASTEL, IRAP, Universite´ de Toulouse 3 - CNRS - OMP, Toulouse, France.

The story of a Solar type system starts from an initial molecular clump and ends up into a specific planetary system, with its bag of organic complexity acquired during its evolution. In the first step, the so-called prestellar core phase, the WG03 2:39 – 2:54 grains become coated with icy mantles, containing simple hydrogenated molecules and perhaps more complex ones. The AN ALMA SUB-ARCSECOND VIEW OF MOLECULAR GAS IN MASSIVE STAR-FORMING REGION G10.6-0.4 molecules composing these mantles are crucial for the subsequent chemical development, since they constitute the bricks for more complex organic molecules. In a second step, when the collapse sets in, a central source is formed and heats up the CHARLES JOHN LAW, Department of Astronomy, Harvard University, Cambridge, MA, USA;QIZHOU dust around, likely surrounded by a circumstellar disk where the process of planet formation starts. Simultaneously with the ZHANG, Radio and Geoastronomy Division, Harvard-Smithsonian Center for Astrophysics, Cambridge, MA, collapse, material is ejected outwards causing shocks along the path. Heat and shocks release the content of the icy dust USA;KARINIOBERG,¨ Department of Astronomy, Harvard University, Cambridge, MA, USA;ROBERTO mantles into the gas, triggering a series of reactions that perhaps synthesize more complex molecules in the gas. A plethora of GALVAN-MADRID,´ Centro de Radioastronom´ıa y Astrof´ısica, Universidad Nacional Autonoma´ de Mexico,´ complex molecules are observed in hot corinos and molecular shocks. Probably, these molecules subsequently freeze-out into Morelia, Michoacan,´ Mexico;ERICKETO,Institute for Theory and Computation, Harvard-Smithsonian Center icy mantles in the denser and coldest zones of the protoplanetary disk and are “passed on” to the forming planets, comets and for Astrophysics, Cambridge, MA, USA; PAUL T. P. HO, HAUYU BAOBAB LIU, Academia Sinica Institute of asteroids. Thus, the questions that astrochemical community needs to answer to build a reliable theory of the dawn of organic Astronomy and Astrophysics, Academia Sinica, Taipei, Taiwan. chemistry are: Which organic molecules are formed, where, when and how? The discovery of COMs (Complex Organic Molecules) in Solar type hot corinos demonstrated that molecular complexity is not an exclusive prerogative of high mass hot While massive star-forming regions are known to exhibit an extremely rich and diverse chemistry, few such sources have cores and, most important, setting a direct link between organic chemistry in the interstellar medium and in the Solar System. been mapped at high spatial resolution. Since the chemical structure of these sources displays substantial spatial variation More recently came the discovery that COMs can be also present in prestellar cores, against theoretical expectations, and in among species on small scales (∼104 AU), high spatial resolution observations are needed to constrain chemical evolution outflow shocks close to Solar type forming stars. I will present the results from 2 IRAM Large Programs (ASAI and SOLIS) models of massive star formation. We will present new ALMA 1.3 mm observations toward massive OB cluster-forming on the chemical composition of Solar-like protostars and will then present the need for a much higher spatial resolution. region G10.6-0.4 at a resolution of 0.12 (600 AU). While the kinematics of G10.6 have been extensively studied at cen- This need will be covered by the FAUST ALMA Large Program (http://stars.riken.jp/faust/fausthome.htm), which attacks the timeter wavelengths, sensitive and high angular resolution observations in the millimeter and submillimeter regime have been issue of the chemical diversity of young Solar-like systems at planet-formation scales (50 au). I will also present how the lacking. Given the high sensitivity and bandwidth of our ALMA observations, we are able to derive rotational temperature community is organizing to develop tools, useful for an easy line identification in spectral surveys, as well as their links with and column density maps toward the central 8 by 8 region of G10.6 for over 10 different species, including traditional radiative transfer modelling (e.g. CASSIS: http://cassis.irap.omp.eu/). warm gas tracers such as CH3CN, shock tracers HNCO and SiO, and a variety of complex organic molecules. Combined with our simultaneous observations of ionized gas in hydrogen recombination lines, our exquisite spatial resolution allows us to constrain the chemical influences of massive stellar feedback in the form of highly structured and inhomogeneous molec- ular emission, prominent spatial anti-correlations between molecular and ionized gas, and order-of-magnitude variations in physical gas conditions. 160 161

WG04 2:57 – 3:12 WG06 4:09 – 4:24

CONSTRAINING COSMIC-RAY IONIZATION RATES AND CHEMICAL TIMESCALES IN MASSIVE HOT CORES PURE ROTATIONAL STUDY OF CYANOPHENYLACETYLENE (C6H5C3N)

CHRISTOPHER J BARGER, Departments of Chemistry and Astronomy, University of Virginia, Charlottesville, ZACHARY BUCHANAN, Department of Chemistry, The University of California, Davis, CA, USA;OLIVIA VA, USA; ROBIN T. GARROD, Departments of Chemistry and Astronomy, The University of Virginia, Char- CHITARRA, Institut des Sciences Moleculaires´ d’Orsay, Universite´ Paris-Sud, Orsay, France; KELVIN LEE, lottesville, VA, USA. Radio and Geoastronomy Division, Harvard-Smithsonian Center for Astrophysics, Cambridge, MA, USA; MICHAEL C McCARTHY, Atomic and Molecular Physics, Harvard-Smithsonian Center for Astrophysics, Cam- Several studies have demonstrated that the cosmic ray ionization rate is highly variable in the interstellar medium. How- bridge, MA, USA; OLIVIER PIRALI, Institut des Sciences Moleculaires´ d’Orsay, Universite´ Paris-Sud, Or- ever, constraints of this rate for several regions including those that contain hot cores are lacking. Hot cores are appealing say, France; MARIE-ALINE MARTIN-DRUMEL, CNRS, Institut des Sciences Moleculaires d’Orsay, Orsay, sources to study given their rich chemical complexity. The chemistry of these cores can be influenced by both their cos- France. mic ray ionization rates and their warm-up timescales, however, understanding the chemical response to these parameters requires further investigation. We study these effects using the astrochemical hot-core modeling code MAGICKAL, in which The reaction of cyano radical with hydrocarbon chains and rings is thought to be important in the formation of complex we construct a grid of 81 models using nine ionization rates and nine warm-up timescales. We also simulate LTE radiative nitriles, particularly in the formation of polycyclic aromatic hydrocarbons (PAHs). Difficulties in studying these reactions transfer for these models to obtain results that can be directly compared with observations. We compare molecular emission arise from both the plethora of possible product channels, and gaps in our knowledge as to the key species in each pathway. a of these models with observations toward NGC 6334 IRS 1, NGC 7538 IRS 1, W3(H2O), and W33A in an effort to con- One reaction that has been studied in some detail is cyano radical with phenylacetylene. One of the products identified strain their cosmic ray ionization rates and warm-up timescales. Our best fits to the observations suggest that these sources in this reaction is cyanophenylacetylene (3-Phenyl-2-propynenitrile, C6H5C3N), the rotational spectrum of which has not possess elevated cosmic ray ionization rates compared to the canonical value used in previous modeling studies, and rapid been previously studied. Motivated in part by the recent detection of benzonitrile in the ISM,b and the presence of large c warm-up timescales. We also demonstrate that there exists a strong correlation among the cosmic ray ionization rate and cyanopolyyne chains there, , the pure rotational spectrum of C6H5C3N has been investigated in the 8–18 GHz and 75–220 the total hydrogen column density of a source, and a strong correlation among the warm-up timescale and total source mass. GHz regions. We will present our results (experimental spectrum and rotational constants), and discuss the various methods Furthermore, these relationships are in good agreement with other theoretical studies. we used in fitting the data. The new data now allow a search for this species in the ISM.

aBennett et al., Phys. Chem. Chem. Phys. 12, 8737-8749 (2010) bMcGuire et al., Science 359, 202–205 (2018) cBroten et al., ApJL 223, L105-L107 (1978)

WG05 3:15 – 3:30 INTERSTELLAR GLYCOLALDEHYDE, METHYL FORMATE, AND ACETIC ACID: BI-MODAL ABUNDANCE PAT- TERNS IN STAR-FORMING REGIONS

SAMER EL-ABD, Department of Astronomy, The University of Virginia, Charlottesville, VA, USA;CRYSTAL WG07 4:27 – 4:42 L. BROGAN, TODD R. HUNTER, NAASC, National Radio Astronomy Observatory, Charlottesville, VA, USA; SEARCHING FOR A NITROGEN-HETEROCYCLE PRECURSOR: THE ROTATIONAL SPECTRUM OF THE β- ERIC R. WILLIS, Department of Chemistry, The University of Virginia, Charlottesville, VA, USA;ROBINT. CYANOVINYL RADICAL GARROD, Departments of Chemistry and Astronomy, The University of Virginia, Charlottesville, VA, USA; BRETT A. McGUIRE, NAASC, National Radio Astronomy Observatory, Charlottesville, VA, USA. SOMMER L. JOHANSEN, Department of Chemistry, The University of California, Davis, CA, USA;MARIE- ALINE MARTIN-DRUMEL, CNRS, Institut des Sciences Moleculaires d’Orsay, Orsay, France;KYLEN. CH OH The photo-dissociation of methanol ( 3 ) in the interstellar medium is still not a particularly well-understood phe- CRABTREE, Department of Chemistry, The University of California, Davis, CA, USA. nomenon. Since many of the radicals that are formed from this process go on to form the C2H4O2 isomers glycolaldehyde, methyl formate, and acetic acid, measuring the relative abundances of these molecules can give us clues as to the rates at While the rotational spectrum of vinyl cyanide (H2CCHCN) was first published in 1959 and has been detected in molecu- which the radicals are produced. Data on the relative abundances of these molecules also has the potential to constrain forma- lar clouds Sgr B2(N) and TMC-1, the cis- and trans-β-cyanovinyl radicals (HCCHCN, CV) not only have not been detected in tion pathways for the molecules that are necessary for life to emerge. For this analysis we derived molecular abundances of the interstellar medium (ISM), their rotational spectra have not previously been reported. These radicals have been implicated the isomers in two massive cores of NGC 6334I using ALMA spectroscopic data, then examined the literature to find every in the low temperature, gas-phase formation of pyridine, making their study critical to questions of whether pyridine and other source for which at least two of the isomers had measured column densities. This resulted in 15 total sources among which N-containing heterocycles can form in cold molecular clouds. Currently there have been no astronomical detections of N- we could compare relative abundances of the C2H4O2 isomers. heterocycles anywhere in the ISM. Here we present the theoretical equilibrium geometries calculated at the CCSD(T)/ANO1 level and the rotational spectra of both cis- and trans-β-CV from 5 to 80 GHz. These results will support future spectroscopy in the millimeter-wave region, astronomical searches, and kinetics and dynamics studies of N-heterocycle formation.

Intermission 162 163

WG08 4:45 – 5:00 WH. Mini-symposium: Non-covalent Interactions GOTHAM AND ARKHAM: FIRST RESULTS FROM PROGRAMS TO EXPLORE AROMATIC CHEMISTRY AT THE EARLIEST STAGES OF STAR FORMATION Wednesday, June 19, 2019 – 1:45 PM BRETT A. McGUIRE, NAASC, National Radio Astronomy Observatory, Charlottesville, VA, USA;ANDREW M BURKHARDT, , Harvard-Smithsonian Center for Astrophysics, Cambridge, MA, USA; KELVIN LEE, Ra- Room: 100 Noyes Laboratory dio and Geoastronomy Division, Harvard-Smithsonian Center for Astrophysics, Cambridge, MA, USA;RYAN LOOMIS, NAASC, National Radio Astronomy Observatory, Charlottesville, VA, USA; STEVEN B CHARN- LEY, MARTIN CORDINER, Astrochemistry, NASA Goddard Space Flight Center, Greenbelt, MD, USA;ERIC Chair: Mar´ıa Mar Quesada-Moreno, Deutsches Elektronen-Synchrotron, Hamburg, Germany HERBST, Department of Chemistry, The University of Virginia, Charlottesville, VA, USA; SERGEI KALEN- SKII, Astro Space Center, Lebedev Physical Institute, Russian Academy of Sciences, Moscow, Russia;CHRISTO- PHER N SHINGLEDECKER, The Center for Astrochemical Studies, Max-Planck-Institut fur¨ extraterrestrische Physik, Garching, Germany; ERIC R. WILLIS, CI XUE, Department of Chemistry, The University of Vir- ginia, Charlottesville, VA, USA; ANTHONY REMIJAN, NAASC, National Radio Astronomy Observatory, Char- lottesville, VA, USA; MICHAEL C McCARTHY, Atomic and Molecular Physics, Harvard-Smithsonian Center for Astrophysics, Cambridge, MA, USA.

We will present an overview of the GOTHAM (GBT Observations of TMC-1: Hunting Aromatic Molecules) and ARKHAM (A Rigorous K-band Hunt for Aromatic Molecules) projects on the 100 m Robert C. Byrd Green Bank Tele- scope, and a number of first results. These observations, prompted by our earlier detection of benzonitrile (c-C6H5CN)in TMC-1, are designed to probe the extent of hidden chemical complexity at the earliest stages of the star formation process. We will discuss the detections of new molecules in TMC-1, comment on the prospects for probing additional aromatic chem- istry in this source, and examine the apparently widespread nature of benzonitrile through the early protostellar phase of star formation. WH01 1:45 – 2:00 WG09 5:03 – 5:18 JET-COOLED HIGH RESOLUTION INFRARED LASER SPECTROSCOPY OF Kr-H2O IN THE REGION OF THE MILLIMETER-WAVE SPECTROSCOPY OF FLEXIBLE ORGANIC MOLECULES AND COMPARISON WITH AS- BENDING MODE OF H2O TRONOMICAL SURVEYS YACINE BELKHODJA, PIERRE ASSELIN, YANN BERGER, CNRS, De la Molecule´ aux Nano-Objets: SONIA MELANDRI, ASSIMO MARIS, LUCA EVANGELISTI, IMANOL USABIAGA, Dipartimento di Reactivit´ e,´ Interactions, Spectroscopies, MONARIS, Sorbonne Universite´ , PARIS, France. Chimica G. Ciamician, Universita` di Bologna, Bologna, Italy; CAMILLA CALABRESE, Departamento de The high sensitivity of our experimental setup (SPIRALES) [1] which couples an external cavity quantum cascade laser Qu´ımica F´ısica, Universidad del Pa´ıs Vasco (UPV-EHU), Bilbao, Spain;LAURAB.FAVERO,Istituto per lo −1 tunable from 1620 to 1690 cm to a pulsed jet enabled the recording of a series of rovibrational transitions of Kr-H2Ovan Studio dei Materiali Nanostrutturati, Consiglio Nazionale delle Ricerche (ISMN-CNR), Bologna, Italy. der Waals (vdW) complex. As for the Ar-H2O complex [2], the barriers to internal rotation in the Kr-H2O complex states are The identification and quantification of molecules in space is based on spectroscopic methods (in particular rotational comparable to the H2O rotational constants and so the H2O subunit behaves like a nearly free internal rotor [3]. The quantum Σ Π spectroscopy) and laboratory work is essential to provide the community with the spectral features needed to analyze the number K is used for describing the projection of J onto the vdW axis, with K = 0 for ,K=1for , etc. A previous cosmological surveys. Many of the molecules which are searched for in space, are complex organic molecules which show jet-cooled microwave study [4] evidenced that the ground vibrational state involves 2 internal rotor states corresponding to Σ( Σ( a high degree of molecular flexibility. The high number of low energy conformations and the presence of large amplitude different spin modifications, namely a para state 000) and an ortho state 101). The present work reports the observation cm−1 cm−1 motions on shallow potential energy surfaces are peculiar to this kind of systems giving rise to very complex rotational of two new bands around 1634.5 and 1659.7 which can be interpreted according to a pseudo-atomic model. By Π spectra, which represent a challenge for spectroscopic and computational methods. Spectroscopic strategies for the rotational analogy with Ar-H2O bands observed in the same regions [2], the Kr-H2O ones are tentatively assigned to para (111) ← Σ Π ← Σ study of flexible organic molecules include the use of the cold and isolated conditions of a free jet expansion and heated (000) and ortho (212) (101) transitions, respectively, confirmed by the presence of Q branches. The ortho band Σ Π sources for the non-volatile systems while the computational methods must deal with complex conformational surfaces and displays strongly unequal spacings characteristic of a Coriolis coupling between and states in vibrational excited states. large amplitude motions which can cause tunneling splittings of the rotational transitions. As examples, we will discuss Moreover the high resolution achieved with the SPIRALES set- 84Kr the complex conformational space of 1,2-butandiol and the problem of internal rotation in thioacetamide investigated by up allowed the observation of several isotopes of Kr. The analy- Q(11) Q(1) 83 82 sis of these two bands and further investigations in the 1580-1620 86Kr Kr Kr rotational spectroscopy in the 60-118 GHz range −1 cm region are undergoing. 1660.70 1660.80 1660.90 1660.070 1660.085 1660.100 References : [1] P. Asselin , A. Potapov, A. C. Turner, V. Boudon, L. Bruel, M.-A. Gaveau, M. Mons. PCCP 19, 17224-17232 (2017). [2] X. Liu , Y. Xu. J. Mol. Spectr. 301, 1-8 (2014). [3] R.C. 1658.5 1659.0 1659.5 1660.0 1660.5 1661.0 1661.5 Cohen , K . L . Busarow , Y. T. Lee, R. J. Saykally. JCP, 92, 169-177 Wavenumber cm−1 (1990). [4] J. Van Wijngaarden, W. Jager.¨ Mol. Phys. 98, 19,1575- 1588 (2000). 164 165

WH02 2:03 – 2:18 WH04 2:39 – 2:54 THE WATER–CARBON MONOXIDE DIMER: NEW INFRARED SPECTRA, AB INITIO ENERGY LEVEL CALCULA- INFRARED BANDS OF CS2 DIMER AND TRIMER AT 4.5 μm TIONS, AND A CURIOUS INTERMOLECULAR MODE A. J. BARCLAY, KOOROSH ESTEKI, Department of Physics and Astronomy, University of Calgary, Calgary, A. J. BARCLAY, KOOROSH ESTEKI, Department of Physics and Astronomy, University of Calgary, Cal- AB, Canada; K. H. MICHAELIAN, CanmetENERGY, Natural Resources Canada, Edmonton, Alberta, Canada; gary, AB, Canada; BOB McKELLAR, Steacie Laboratory, National Research Council of Canada, Ottawa, ON, BOB McKELLAR, Steacie Laboratory, National Research Council of Canada, Ottawa, ON, Canada;NASSER Canada; NASSER MOAZZEN-AHMADI, Physics and Astronomy/Institute for Quantum Science and Technol- MOAZZEN-AHMADI, Physics and Astronomy/Institute for Quantum Science and Technology, University of ogy, University of Calgary, Calgary, AB, Canada. Calgary, Calgary, AB, Canada.

Weakly-bound H2O-CO has a planar structure with approximately co-linear heavy atoms (O, C, O) and a hydrogen bond We report observation of new infrared bands of (CS2)2 and (CS2)3 in the region of the CS2 ν1 + ν3 combination band (at between the water and the carbon of the CO. Proton tunneling (H atom interchange) gives rise to two states corresponding 4.5 μm) using a quantum cascade laser. The complexes are formed in a pulsed supersonic slit-jet expansion of a gas mixture −1 to distinct nuclear spin modifications. The magnitude of the splitting in the ground rotational state is about 0.8 cm for of carbon disulfide in helium. We have previously shown that the most stable isomer of (CS2)2 is a cross-shaped structure −1 H2O-CO and 0.04 cm for D2O-CO. Due to the almost linear heavy atom configuration, H2O-CO has a large A rotational with D2d symmetry and that for (CS2)3 is a barrel-shaped structure with D3 symmetry. The dimer has one doubly degenerate −1 −1 constant, equal to about 19 cm (12 cm for D2O-CO), so the K quantum number is highly significant. Water-CO was first infrared-active band in the ν1 + ν3 region of the CS2 monomer. This band is observed to have a rather small vibrational shift studied in the microwave and millimeter regions. Infrared spectra have been observed in the regions of the C-O stretch, the of -0.846 cm−1. We expect one parallel and one perpendicular infrared-active band for the trimer but observe two parallel −1 −1 O-H stretch, the D2O bend, and the H2O bend. Here we study the O-D stretch region (3.6 μm) for the first time, observing and one perpendicular bands. Much larger vibrational shifts of -8.953 cm for the perpendicular band and -8.845 cm and −1 D2O-CO, HOD-CO, and DOH-CO. We also extend the C-O stretch region results to include the K = 1 ← 0 subbands, thus +16.681 cm for the parallel bands are observed. Vibrational shifts and possible vibrational assignments, in the case of the determining A rotational constants for the v(CO) = 1 excited state. But more significantly, we also observe additional K = 1 parallel bands of the trimer, are discussed using group theoretical arguments. ← 0 combination bands in both regions which involve the lowest intermolecular vibration of water-CO. This mode, which lies −1 at 43 – 49 cm depending on isotopologue, can be identified as the in-plane CO bend. It is observed for H2O-CO, D2O-CO, and HOD-CO, and exhibits anomalous isotope shifts: even though their A-values are quite different, the D2O-CO mode is only slightly lower in energy than that of H2O-CO. Detailed rotational energy level calculations, based on a recent high-level ab initio potential energy surface a, are in good agreement with experiment, including the newly observed intermolecular mode. As well, the calculations show that the unobserved K = 0 level of this mode lies above the observed K = 1 level, thus explaining the anomalous isotope shifts.

aY. N. Kalugina, A. Faure, A. van der Avoird, K. Walker, and F. Lique, Phys. Chem. Chem. Phys. 20, 5469 (2018).

WH05 2:57 – 3:12 IN SITU STUDIES OF ELECTROCHEMICAL REACTIONS USING VIBRATIONAL SUM FREQUENCY GENERA- TION

SPENCER WALLENTINE, SAVINI SANDUNIKA BANDARANAYAKE, ROBERT BAKER, Department of WH03 2:21 – 2:36 Chemistry and Biochemistry, The Ohio State University, Columbus, OH, USA. NH INTERNAL ROTATION OF INTRAMOLECULAR HYDROGEN BONDING OF OH OR 2 GROUPS ATTACHED TO Electrochemical reactions play important roles in chemical energy conversion. However, the surface reactions that govern a THREE-MEMBERED RING MOLECULES these processes are not well understood because of the difficulties associated with accessing the electrode/electrolyte inter- face and making chemically specific measurements with interface sensitivity. Vibrational spectroscopy offers the required ESTHER JULIANA OCOLA, JAAN LAANE, Department of Chemistry, Texas A & M University, College Sta- chemical specificity and can be used to elucidate reaction pathways based on the formation of key functional groups along tion, TX, USA. a reaction coordinate. However, the challenge is to implement infrared spectroscopy as a surface sensitive probe at the elec- trode/electrolyte interface. Vibrational sum frequency generation spectroscopy is an inherently interface specific technique, The internal rotations about the single bonds connecting OH or NH2 groups to cyclopropyl or cyclopropene rings were investigated. The experimental fits to the infrared data of the one-dimensional torsional potential energy functions were but most people who study electrode/electrolyte interfaces employ a thin film of electrolyte which leads to wavelength- compared to theoretical calculations. MP2/cc-pVTZ and CCSD/cc-pVTZ computations were found to be in good agreement dependent attenuation of the infrared field and also presents mass transport limitations when seeking to probe electrocatalytic with the experimental results for cyclopropanol and cyclopropylamine. Calculations were also carried out on the internal reaction kinetics. We present a method to overcome these limitations with high signal quality and under conditions that are rotations of 1-cyclopropen-1-ol and 2-cyclopropen-1-amine. Each of these molecules has a calculated energy minimum compatible with electrocatalysis at high current densities. Under these conditions we study CO2 reduction on polycrystalline corresponding to a conformation with an intramolecular π-type hydrogen bond. The π-bonding stabilization is 2.3 kcal/mol gold thin films and gold nanoparticles which show faradaic efficiencies for carbon monoxide of 20% and 60% respectively. for the alcohol and 2.5 kcal/mol for the amine. The calculated O-H, N-H, and C=C stretching frequencies are lower for We identify possible reasons for the observed difference in selectivity. the hydrogen bonded conformers than for the conformations without the π-type hydrogen bonds. The C=C bond stretching frequencies show the largest decreases resulting from the hydrogen bonding.

aThe authors wish to thank the Robert A. Welch Foundation (Grant A-0396) for financial support.

Intermission 166 167

WH06 3:51 – 4:06 WH09 4:45 – 5:00 THEMOSTSTABLEISOMEROFC4H2-(OCS)2 VAN DER WAALS COMPLEX: THEORY AND EXPERIMENT CON- WEAKLY-BOUND COMPLEXES OF THIOPHENE AND WATER AS INVESTIGATED BY MATRIX ISOLATION FTIR FIRM A STRUCTURE WITH C2 SYMMETRY AND COMPUTATION

A. J. BARCLAY, Department of Physics and Astronomy, University of Calgary, Calgary, AB, Canada;AN- JOSHUA G WASSERMAN, KESHIHITO J MURPHY, JOSH NEWBY, Department of Chemistry , Hobart and DREA PIETROPOLLI CHARMET, Dipartimento di Scienze Molecolari e Nanosistemi, Universita` Ca’ Foscari, William Smith Colleges, Geneva, NY, USA. Venezia, Italy; BOB McKELLAR, Steacie Laboratory, National Research Council of Canada, Ottawa, ON, Canada; NASSER MOAZZEN-AHMADI, Physics and Astronomy/Institute for Quantum Science and Technol- Weakly-bound complexes containing aromatic species have been the subject of study for many years. Here, a study ogy, University of Calgary, Calgary, AB, Canada. of the weakly-bound complexes of thiophene (C4H4S) with water will be presented. In this study, matrix isolation FTIR and computational methods were used to examine stable 1:1 complexes of thiophene : water (Tp:H2O). Multiple density We report the infrared spectrum of C4H2-(OCS)2 trimer in the region of the ν1 fundamental vibration of the OCS functional theories along with MP2 calculations were used to find four stable geometries. Two geometries can be described monomer. The van der Waals complexes are generated in a supersonic slit-jet apparatus and probed using a rapid-scan by C−H···O interaction, one by O−H···π interaction, and one by O−H···S interaction. These geometries were found to be tunable diode laser. Both C4H2-(OCS)2 and C4D2-(OCS)2 are studied. Analysis of their spectra establishes that the trimer within 10 kJ/mol of each other by all computational methods. Matrix isolation FTIR experiments identified several peaks has C2 symmetry. Theoretical calculations performed to find stationary points on the potential energy surface confirm that that were not associated with isolated water or thiophene, implying the bands are due to weakly-bound complexes of the two. the experimental structure is the most stable form of the trimer. The rotational parameters computed using double hybrid In addition to normal water, D2O and HDO complexes with thiophene were also observed. Possible interpretations of the a functionals are in very good agreement with those obtained from the observed spectra. experimental and computational results will be presented. Comparisons to the structure of furan (C4H4O) : water will also be discussed. WH07 4:09 – 4:24 aLockwood, S. P.; Fuller, T. G.; and Newby, J. J. J. Phys. Chem. A 2018, 122, 36, 7160-7170 LASER SPECTROSCOPY OF OCS-WATER COMPLEXES IN SUPERFLUID HELIUM NANODROPLETS WH10 5:03 – 5:18 ISAAC JAMES MILLER, TYLER WELLS, TY FAULKNER, PAUL RASTON, Chemistry and Biochemistry , James Madison University, Harrisonburg, VA, USA. INFRARED PHOTODISSOCIATION SPECTROSCOPY OF PROTONATED AMMONIA CLUSTERS IN THE GAS PHASE Superfluid helium nanodroplets are particularly useful for synthesizing molecular complexes, and several investigations have focused on investigating the hydration of atmospherically important molecules, such as the hydroxyl radical [1]. While JASON E. COLLEY, J. PHILIPP WAGNER, MICHAEL A DUNCAN, Department of Chemistry, University of carbonyl sulphide is the most abundant sulphur containing molecule in the atmosphere, little is known experimentally about Georgia, Athens, GA, USA. how it interacts with water. In this study we focus on isolating OCS-(H2O) complexes in helium nanodroplets, and on N The clustering of protonated ammonia clusters, a known interstellar ion, are studied with infrared photodissociation spec- uncovering their infrared signatures with quantum cascade laser spectroscopy. For the dimer, we identified two isomers, −1 + troscopy in the region of 4700 to 7200 cm .H (NH3) clusters up to n=8 are produced using a pulsed electrical discharge which is consistent with what was observed in solid neon [2]. One of the isomers has C symmetry with the water near the n s in a supersonic expansion. Mass-selected ions are investigated using tunable infrared laser photodissociation in the turning oxygen end of OCS, and the other has C2 symmetry, with the water at the sulphur end. The latter isomer displays well v region of a reflectron time of flight mass spectrometer. Clusters of protonated ammonia are probed through the dissociative resolved rotational substructure in its C-O stretching band, and Stark spectroscopy has been performed, which should allow elimination of an ammonia. The spectra gathered were assigned by comparing to B2PLYP/def2-TZVP computations. Two for determination of its dipole moment. Larger clusters seem to build off of the dimers, as evidenced by two sets of infrared −1 bands are consistently observed for the studied protonated ammonia clusters. A band at around 5000 cm is attributed to a bands that grow in with increasing water concentrations, near the corresponding OCS-H2O bands. −1 combination of the N-H stretching and bending modes. Another band at around 6500 cm is assigned to either an overtone [1] F. J. Hernandez et al. The Journal of Chemical Physics 143, 164304 (2015). [2] P. Soulard et al. The Journal of or a combination of the N-H stretching modes. Chemical Physics 146, 234303 (2017).

WH08 4:27 – 4:42 CHARACTERIZATION OF A HYDROGEN PEROXIDE-BENZENE COMPLEX USING MATRIX ISOLATION IN- FRARED SPECTROSCOPY

JAY C. AMICANGELO, DYLAN JOHNSON, CATHERINE KAISER, YUDHISHTARA PAYAGALA, JACOB OSLOSKY, LIA TOTLEBEN, School of Science (Chemistry), Penn State Erie, Erie, PA, USA.

Matrix isolation infrared spectroscopy was used to characterize a 1:1 complex of hydrogen peroxide (H2O2) with ben- zene (C6H6). Co-deposition experiments with H2O2 and C6H6 were performed at 20 K using argon as the matrix gas. New infrared peaks attributable to the H2O2-C6H6 complex were observed near the O-H stretching vibrations and the OH bending vibrations of the H2O2 monomer and near the hydrogen out-of-plane bending vibration of the C6H6 monomer. The initial identification of the newly observed infrared peaks to those of a H2O2-C6H6 complex was established by performing several concentration studies in which the sample-to-matrix ratios of the monomers were varied between 1:100 to 1:1600, by compar- ing the resulting co-deposition spectra with the spectra of the individual monomers, and by matrix annealing experiments (30 – 35 K). Co-deposition experiments using isotopically labeled hydrogen peroxide (D2O2 and HDO2) and benzene (C6D6) in argon were also performed and the analogous peaks for the isotopically labelled complexes were observed. A series of co-deposition experiments with H2O2 and C6H6 was also performed using nitrogen as the matrix gas. Quantum chemical calculations were performed for the H2O2-C6H6 complex at the MP2/aug-cc-pVDZ and M06-2X/aug-cc-pVDZ levels of theory in order to obtain optimized complex geometries and predicted vibrational frequencies of the complex, which were compared to the experimental infrared spectra. 168 169 WI. Structure determination Wednesday, June 19, 2019 – 1:45 PM WI04 2:39 – 2:54 Room: 1024 Chemistry Annex CONFORMATIONAL ANALYSIS OF γ-HEXANOLACTONE BY MICROWAVE SPECTROSCOPY Chair: M. Eugenia Sanz, King’s College London, London, United Kingdom TAKAHIRO TAKIMOTO, NOBUHIKO KUZE, YOSHIYUKI KAWASHIMA, Department of Materials and Life Sciences, Sophia University, Tokyo, Japan. WI01 1:45 – 2:00 IDENTIFYING THE DIFFERENCES IN CONJUGATED VS. NON-CONJUGATED BIOMOLECULES IN CANCER RE- γ-Hexanolactone (5-ethyldihydro-2-furanone) (γ-HL) is an odor molecule that is included in a natural food such as SEARCH USING VIBRATIONAL SPECTROSCOPY pineapple. The rotational spectra of γ-HL were observed by a Fourier transform microwave spectrometer combined with a heated nozzle of 303 K. The three conformers in expected to six were observed.For the first conformer, 65 a-type, 48 b-type, ROBINSON KARUNANITHY, TORREY E. HOLLAND, P SIVAKUMAR, Physics, Southern Illinois Univer- and 22 c-type transitions were assigned. Similarly, 41 a-type, 40 b-type, and 12 c-type transitions for the second one were sity Carbondale, Carbondale, IL, USA. assigned and 50 a-type and 34 b-type transitions for the third one. A comparison of the observed rotational constants with those calculated by ab initio MO method led us to conclude that the second conformer is the eq-T in which an ethyl group Biomarkers are critical tools employed in cancer research, as diagnostic implements in the early detection of cancer. attached to C(5) is in an equatorial position (eq), where T and G denote the conformations about the C(6)-C(5) bond, with Successful bioconjugation is vital for improving the sensitivity and specificity in which it requires for the early detection of T and G designating trans and gauche, respectively. We identified that the first and third conformers are eq-G’ and eq-G, ovarian cancer. This study aims to understand the bioconjugation process by studying molecular interactions with Raman and respectively, because of absence of the c-type transitions and large pseudo-inertial defect for third one. The eq-G’ of the γ- FT-IR spectroscopies. In each bioconjugation stage, we explore the molecular structure change by analyzing the vibrational HL was calculated to be the most stable. The splittings due to internal rotation of the methyl group were observed for all the signature of molecular bond to improve the coupling efficiency. Specifically, this study is looking at the differences after three conformers and were analyzed by the XIAM program. The rotational constants thus derived agree with the predictions successful coupling of amine coated iron particles with glutaraldehyde and avidin and glutaraldehyde. made by quantum chemical calculations, MP2/6-311++G(d,p) within 0.9%.

WI02 2:03 – 2:18 WI05 2:57 – 3:12 CONFORMATION-SPECIFIC IR AND UV SPECTROSCOPY OF A SERIES OF SYNTHETIC FOLDAMERS: α/β3- FOURIER TRANSFORM MICROWAVE SPECTRA OF 1-PENTANETHIOL AND β3- ALA DIPEPTIDES KOJIRO SUZUKI, NOBUHIKO KUZE, YOSHIYUKI KAWASHIMA, Department of Materials and Life Sci- DEWEI SUN, KARL N. BLODGETT, JOSHUA L. FISCHER, TIMOTHY S. ZWIER, Department of Chemistry, ences, Sophia University, Tokyo, Japan. Purdue University, West Lafayette, IN, USA. Rotational spectra of the 1-pentanethiol (1-C5SH) were observed using a Fourier transform microwave spectrometer. With the development of designed foldamers that display biological activity and aid in drug delivery processes, there Eight sets of the 1-C5SH were assigned by combined with the quantum chemical calculations. The four Sets 1-4 of a-type is an increasing interest in exploring the inherent conformational properties of model foldamers to understand better the R-branch transitions of 1-C5SH were observed in diluted Ar. Another four Sets 5-8 of a-type transition were observed near subtle counter-balance of forces at play β-amino acids have one additional backbone carbon atom that extends the spacing the four Sets 1-4 in diluted Ne instead of Ar. The Set 1 has the most intense spectrum and small splittings due to the between amide groups, thereby providing flexibility in construction of β-andα/β- peptides, leading to secondary structures torsional motion of the SH group and the internal rotation of the CH3 group of the TTTg conformer of the 1-C5SH. In the that either mimic or are complementary to those found in nature. Here we explore the conformational preferences of a series case of 1-C5SH there are four operations; the first generating operation is the relative orientation of CH3 groups around the of β-andα/β- dipeptides under jet-cooled conditions in the gas phase. The molecules are brought into the gas phase using C(5)H3C(4)H2-C(3)H2C(2)H2C(1)H2SH axis, leading to gauche and trans conformers, G or T, the second is around C(3)- laser desorption. Our studies include two capped α/β - dipeptides, Ac-L-Ala-β3-(R)-hAla-NHBn and Ac-β3-(R)-hAla-L- C(2) axis and the third is around C(2)-C(1) axis, leading to gauche and trans conformers, G, G’ or T, and the fourth is around Ala-NHBn as structural isomers, and one capped pure β3-dipeptide, Ac-(R)-hAla-β3-(S)-hAla-NHBn . By incorporating C(1)-SH also leading to gauche and trans orientations, g, g’ or t.ForSet2,a-, b-, and c-type transitions were observed and an NHBn cap, a UV chromophore is present that can be used to record resonant two-photon ionization (R2PI) spectra. assigned as to TTGg’ conformer. Only a-type transitions of the Sets 3 and 4 were observed. The obtained rotational constants Conformation-specific infrared and ultraviolet spectra are then recorded using resonant ion-dip infrared (RIDIR) and IR-UV of the Sets 3 and 4 agreed with the calculated values of the TGTg/TGTg’ and GTTg/GTTg’, respectively. Comparing the hole burning spectroscopies, respectively. With this set of peptides, we are able to probe the effect of a chirality switch at obtained rotational constants with the quantum chemical calculations, the Sets 5 and 6 were assigned as to be TTTt and TTGg, a single chiral center on inherent local conformational preferences. Following an exhaustive computational search of the respectively. Similarly Sets 3, 7, 4 and 8 were assigned as TGTg’, TGTg, GTTg and GTTg’, respectively. conformational potential energy surface, low-lying minima are optimized and IR spectra calculated for comparison with the experimental RIDIR spectra provide conformational assignments. Lowest-energy conformers are observed for the α/β- WI06 3:15 – 3:30 3 peptides and assigned to C7/C8 (C8/C7) hydrogen-bonded architectures, while for the pure β -peptide analog, only one BROADBAND MICROWAVE SPECTROSCOPY OF TRANS 3-PENTENENITRILE AND ITS PYROLYSIS PRODUCTS conformer is observed experimentally and assigned to a C12 hydrogen-bonded architecture. PIYUSH MISHRA, SEAN FRITZ, BRIAN M HAYS, TIMOTHY S. ZWIER, Department of Chemistry, Purdue University, West Lafayette, IN, USA. WI03 2:21 – 2:36 FOURIER TRANSFORM MICROWAVE SPECTRUM OF CIS-3-HEXENAL Titan, a moon of Saturn, has an atmosphere that is similar to prebiotic earth, which is nitrogen rich. Pentenenitriles are of importance as they are potential precursors to hetro-aromatic compounds like pyridine. This talk will describe our broadband SEIYA YOSHIZAWA, NOBUHIKO KUZE, YOSHIYUKI KAWASHIMA, Department of Materials and Life microwave studies of trans 3-pentenenitrile (t-3PN) under jet-cooled conditions. Strong-field coherence breaking (SFCB) was Sciences, Sophia University, Tokyo, Japan. used to selectively modulate the intensities of microwave transitions in a conformer-specific manner, aiding analysis. Two conformers of t-3PN were identified and the rotational transitions were assigned. The talk will compare the conformational The cis-3-hexenal (c3-HA) is known as an odor molecule of grass and that the c3-HA easily isomerizes to trans-2-hexenal preferences of 3-pentenenitrile with its isomer, 4-pentenenitrile, previously studied in our laboratory. (t2-HA). The ground-state rotational spectrum of the c3-HA was observed and analyzed by molecular beam Fourier transform The studies of t-3PN serve as a necessary foundation for subsequent studies of its pyrolysis over the 300K-850K tem- microwave spectroscopy combined with quantum chemical calculations. The sample of the c3-HA is a little unstable in the perature range, using a modified Chen nozzle followed by supersonic expansion. We combined CP-FTMW instrument with metal nozzle because the observed spectrum of the c3-HA was getting weaker and then the rotational spectra of the t2-HA vacuum ultraviolet (VUV) time-of-flight mass spectrometry (TOF-MS) to obtain mass-correlated broadband microwave spec- appeared. We identified one conformer: the cis-S’GS’,whereS’, G, and S’ denote the skew’ around the OC(1)-C(2)H2 axis, tra. The temperature dependence of the mass spectra aid in identifying the carriers of new transitions appearing in the mi- gauche around the C(1)C(2)-C(3)C(4) axis, and skew’ around the C(3)C(4)-C(5)C(6) axis, respectively, for which a-type, crowave spectrum. The thermal decomposition of t-3PN produces a range of products, including those that are both radical b-type, and c-type transitions were observed. and molecular in nature. 170 171

Intermission WI10 5:03 – 5:18 THE FEASIBILITY OF DETERMINING THE CARBON FRAMEWORK GEOMETRY OF A MOLECULE FROM ANALYSIS OF THE CARBON-13 ISOTOPOLOGUE ROTATIONAL SPECTRA IN NATURAL ABUNDANCE WI07 4:09 – 4:24 KEVIN J MAYER, BROOKS PATE, ELEANOR PATRINELY, EMMIT PERT, AUSTIN CHENG, KIRA AN INVESTIGATION OF THE NUCLEAR QUADRUPOLE COUPLING TENSORS OF 2-BROMOPYRIDINE USING BAUGH, KEVYN HADLEY, SEAN LEE, GEORGE FAIRMAN, JAKE BUTLER, GAETAN BANAWOE, IG- THE EXTENDED TOWNES-DAILEY ANALYSIS NACIO SIMON, Department of Chemistry, The University of Virginia, Charlottesville, VA, USA. ANGELA Y. CHUNG, ERIC A. ARSENAULT, SUSANNA L. STEPHENS, WALLACE C. PRINGLE, De- One powerful feature of molecular rotational spectroscopy is the ability to obtain quantitative information for the posi- partment of Chemistry, Wesleyan University, Middletown, CT, USA; CARLOS A JIMENEZ-HOYOS, Chemistry tions of individual atoms in the structure through the analysis of singly-substituted isotopologue spectra. However, because , Wesleyan University , Middletown, CT, USA; S. A. COOKE, Natural and Social Science, Purchase College the structural information comes from changes in the moments-of-inertia, the signs of the atom coordinates in the principal SUNY, Purchase, NY, USA; STEWART E. NOVICK, Department of Chemistry, Wesleyan University, Middle- axis system are not available. This project explores the ability to obtain the carbon framework geometry of a molecule from town, CT, USA. isotopologue spectra. The first step of the analysis examines the distributions of carbon-carbon atom distances, C-C-C bond The rotational spectrum of 2-bromopyridine was measured with a cavity FTMW spectrometer, and the complete nuclear angles, and correlations between the bond angles and bond distances found in molecules. The “rules” for acceptable struc- quadrupole coupling tensors of 79Br, 81Br, and 14N were determined. These tensors are interpreted using the Extended tures are obtained through the analysis of about 100 optimized structures from quantum chemistry that were available in lab. N−1 Townes-Dailey (ETD) analysisa. which allows us to predict orbital electron populations. These results are compared to ab These rules are then used to find acceptable carbon framework geometries from the 8 possible carbon frameworks that initio Intrinsic Atomic Orbital (IAO) populations. The ETD analysis for the 14N nucleus requires expressing the orbitals as come from the sign ambiguity of the substitution coordinates. In the test case of a molecule with 6 carbon atoms, cyclohexene sp2 hybrids and performing rotations on the measured quadrupole tensors and the calculated IAO populations. oxide, these rules produced a single (and correct) carbon atom framework from the 32,768 possibilities. For molecules with 12 carbon atoms, a relatively large number of possible carbon atom frameworks are found to be consistent with the structure aS. E. Novick J. Mol. Spectrosc. 267 13-18, 2011. constraints: about 100,000 out of the 8.6 billion possible geometries. The results of the analysis as a function of molecular mass (number of carbon atoms) and structural characteristics (compact structures compared to structures with long alkyl tails, WI08 4:27 – 4:42 for example) will be presented. Approaches to assigning quality scores to candidate carbon atom frameworks that meet the CONCERNING THE GROUND STATE STRUCTURES OF TWO PARTIALLY FLUORINATED CYCLOPENTANES structure conditions with the goal of ranking the most likely molecular structures will also be discussed. C5H3F7 AND C5H2F8

A. J. MINEI, Department of Chemistry and Biochemistry, Division of Natural Sciences, College of Mount Saint Vincent, Riverdale, NY, USA; S. A. COOKE, Natural and Social Science, Purchase College SUNY, Purchase, NY, USA.

The pure rotational spectra of the title compounds have been recorded and ana- lyzed between 8 GHz and 16 GHz. For both species the spectra from all of the singly substituted carbon-13 isotopologues were observed in natural abundance. Ground state rotational constants together with the results of quantum chemical calculations have then been used to investigate the ground state positions of the carbon atoms within each molecule. For both species there is notably poor agreement between the Kraitch- man equation structures and the calculated structures. It is proposed that an isotope- dependent zero-point vibration results in differences between the ground state geome- tries of the carbon-12 and each of the singly substituted carbon-13 rings which, in turn, precludes a satistfactory Kraitchman structural analyses.

WI09 4:45 – 5:00 STRUCTURAL DETERMINATION OF THE CHIRAL MOLECULE 2-BROMO-1,1,1,3-TETRAFLUOROETHANE BY CP-FTMW SPECTROSCOPY

JOSHUA E. ISERT, FRANK E MARSHALL, G. S. GRUBBS II, Department of Chemistry, Missouri University of Science and Technology, Rolla, MO, USA.

Dipole forbidden, nuclear electric quadrupole allowed transitions in microwave spec- troscopy are manifested through a linkage in off-diagonal components of the quadrupole coupling tensor. It is hypothesized that these transitions, due to their transition pathways, could possibly be used to differentiate chirality in a microwave three-wave mixing (3WM)- type experiment. In order to test this hypothesis, 2-bromo-1,1,1,3-tetrafluoroethane was chosen, as it is chiral, possesses a large quadrupolar nucleus and is heavy enough to gen- erate the needed mixing to bring about these forbidden transitions. Because this the first known rotational study of the molecule, traditional rotational spectroscopy utilizing CP- FTMW techniques was performed first. This presentation will describe the collection of spectra, structural analysis, and observed dipole forbidden transitions of the title molecule. 172 173 WJ. Metal containing Wednesday, June 19, 2019 – 1:45 PM WJ03 2:21 – 2:36 EXAMINING THE LOW ENERGY STATES OF NDO+ USING TWO-PHOTON IONIZATION Room: 217 Noyes Laboratory THOMAS D. PERSINGER, ROBERT A. VANGUNDY, MICHAEL HEAVEN, Department of Chemistry, Chair: Caroline Chick Jarrold, Indiana University, Bloomington, IN, USA Emory University, Atlanta, GA, USA.

The auto-ionization reaction Nd + O → NdO+ +e− has been explored as a possible means for controlled modulation of the electron density in the thermosphere. High-altitude Nd release experiments have been conducted using sounding rockets, but the degree of ionization achieved was uncertain. The ionization energy (IE) of NdO is a key parameter for determination of the electron yield from the auto-ionization reaction, and the value available from the literature was of questionable accuracy. Resonantly enhanced two photon ionization (R2PI) was used to remeasure the IE. The value obtained, 5.5083(2) eV, was + WJ01 1:45 – 2:00 0.54 eV higher than previous estimates. Combined with estimates of the NdO bond dissociation energy, our result indicates that the auto-ionization reaction is exothermic by 1.76(10) eV. Low energy states of NdO+ were examined using pulsed- MASS-INDEPENDENT DUNHAM ANALYSIS OF THE KNOWN ELECTRONIC STATES OF PtS field ionization zero kinetic energy photoelectron spectroscopy (PFI-ZEKE). A total of thirty vibronic levels arising from eight electronic states of NdO+ were observed. The pattern of electronic states indicates that the lowest energy electronic JACK C HARMS, Chemistry and Biochemistry, University of Missouri, St. Louis, MO, USA; LEAH C O’BRIEN, 3+ 2− Department of Chemistry, Southern Illinois University, Edwardsville, IL, USA; JAMES J O’BRIEN, Chemistry configuration is Nd (4f3)O , which agrees with electronic structure calculations and ligand field theory models. and Biochemistry, University of Missouri, St. Louis, MO, USA.

+ 3 − + 3 − Several new vibrational bands of the [15.9] B Ω=0 -X Σ(Ω=0+) and [12.5] Ω=0 -X Σ(Ω=0+) transitions of PtS have been recorded at high resolution using Intracavity Laser Spectroscopy (ILS). These new bands have been rotationally analyzed and incorporated into a comprehensive PtS data set that was fit to a mass-independent Dunham expression using PGOPHER. The comprehensive data set included all of the reported spectroscopic data for PtS, including: 32 FTMW transitions (estimated accuracy: 1 kHz) [Cooke and Gerry, J. Chem. Phys., 121, 3486 (2004)], 9 MODR transitions (25 kHz) [Li et al., J. Mol. Spec., 170, 310 (1995)], 51 mm- and sub-mm transitions (25-50 kHz) [Okabayashi et al., J. Mol. Spec., 248, 7 (2012)], 469 MB-LIF transitions (0.003 cm−1)[Liet al.], and 4651 ILS transitions (0.005 cm−1) [Handler et al., J. Mol. Spec., 263, 78 (2010) and from this work]. Deviations from the Dunham model were observed due to both the breakdown of the Born-Oppenheimer approximation and field-shift effects resulting from differences in nuclear charge density between Pt-isotopes. The observed field-shift effects extended to isotope-dependent shifts in electronic excitation energy, which have been reported previously only for PbS (and for PtF and PtCl in recent work by our group). The results of the analysis and a discussion of the deviations from the Dunham model will be presented. WJ04 2:39 – 2:54 IDENTIFICATION OF TWO NEW ELECTRONIC TRANSITIONS OF TaF USING INTRACAVITY LASER SPEC- TROSCOPY

KRISTIN N BALES, JACK C HARMS, Chemistry and Biochemistry, University of Missouri, St. Louis, MO, WJ02 2:03 – 2:18 USA; LEAH C O’BRIEN, Department of Chemistry, Southern Illinois University, Edwardsville, IL, USA;JAMES J O’BRIEN, Chemistry and Biochemistry, University of Missouri, St. Louis, MO, USA. MASS-INDEPENDENT DUNHAM ANALYSIS OF NEW ELECTRONIC TRANSITIONS OF PtX (X=F, Cl) OBSERVED USING INTRACAVITY LASER SPECTROSCOPY Two new electronic transitions of TaF have been recorded at high resolution using Intracavity Laser Spectrscopy (ILS). The TaF molecules were produced in a current-regulated RF discharge operating with 0.35-0.40 A applied to a Ta-lined Cu JACK C HARMS, Chemistry and Biochemistry, University of Missouri, St. Louis, MO, USA; LEAH C O’BRIEN, hollow cathode. The hollow cathode was located within the resonator cavity of a dye laser, tunable over the 14,500-17,200 Department of Chemistry, Southern Illinois University, Edwardsville, IL, USA; JAMES J O’BRIEN, Chemistry cm−1range using DCM and R6G laser dyes. Effective pathlengths from 0.40-2.25 km were utilized with the ILS method. and Biochemistry, University of Missouri, St. Louis, MO, USA. Five bands were observed with red-degraded bandheads near 15,366 cm−1, 16,033 cm−1, 15,630 cm−1, 16,327 cm−1,and cm−1 Ω Ω Several vibrational bands of new electronic transitions of PtF and PtCl have been recorded in absorption using Intracavity 16,930 that have been respectively assigned as the (0,0) and (0,1) bands of the [16.0] =0-X =0 transition of TaF, Ω Ω Laser Spectroscopy (ILS). The PtX molecules were produced in current-regulated RF plasma discharges, operating with 0.30- and (0,1), (0,0), and (1,0) bands of the [16.3] =1-X =0 transition of TaF. Rotational assignments for the transitions have 0.80 A applied to a Pt-lined Cu hollow cathode in approximately 1 Torr of an Ar/He sputter gas mixture. A trace amount been confirmed through combination difference analysis using the reported line positions of Ng et al. [J. Chem. Phys., 146, of SF6 was used as the fluoride source for PtF, and a trace amount of CCl4 was used as the chloride source for PtCl. The 094308 (2017)]. These line positions from Ng et al. were included in the PGOPHER fit of the newly observed transitions. hollow cathode was located within the resonator cavity of either a DCM dye laser (14,500-16,500 cm−1) or Ti:Sapphire laser Results of the analysis will be presented. (12,890-12,990 cm−1; 13,255-13,365 cm−1), and effective pathlengths of 0.4-2.0 km were utilized with the ILS method. Six vibrational bands were identified for PtF and eight vibrational bands were identified for PtCl. These band systems were Ω 2Δ Ω 2Π assigned to the [15.8+x] =5/2-B 5/2 transition of PtF and the [13.8] =3/2-X 3/2 transition of PtCl. Both electronic transitions were fit to a mass-independent Dunham type Hamiltonian using PGOPHER. Isotope dependent deviations from the Dunham model were observed due to both Born-Oppenheimer breakdown and field-shift effects resulting from differences in nuclear charge density between Pt-isotopes. The results of the analyses will be presented.

Intermission 174 175

WJ05 3:33 – 3:48 WJ08 4:27 – 4:42 IDENTIFICATION OF THE FIRST ROTATIONALLY RESOLVED ELECTRONIC TRANSITIONS OF TUNGSTEN SUL- THE 3d BROMIDE SERIES: THE PURE ROTATIONAL SPECTRUM OF CrBr (X6Σ+) FIDE OBSERVED USING INTRACAVITY LASER SPECTROSCOPY TYLER J HERMAN, Department of Chemistry and Biochemistry, University of Arizona, Tucson, AZ, USA; KRISTIN N BALES, JACK C HARMS, Chemistry and Biochemistry, University of Missouri, St. Louis, MO, LUCY M. ZIURYS, Department of Chemistry and Biochemistry, Department of Astronomy, The University of USA; LEAH C O’BRIEN, Department of Chemistry, Southern Illinois University, Edwardsville, IL, USA;JAMES Arizona, Tucson, AZ, USA. J O’BRIEN, Chemistry and Biochemistry, University of Missouri, St. Louis, MO, USA. The millimeter-wave spectrum of the high spin radical chromium bromide, CrBr, in its X6Σ+ state has been measured Six bands have been recorded at high resolution in absorption in the visible using Intracavity Laser Spectroscopy (ILS). using direct absorption methods between 220-300 GHz. The radical was created in a DC discharge by the reaction of di- The bands were observed in the current-regulated RF discharge resulting when 0.30 A was applied to a W-lined Cu hollow bromomethane with chromium vapor, produced in a Broida-type oven. This study is the first measurement of CrBr by any 52 79 52 81 53 79 53 81 cathode, using approximately 300 mTorr of an Ar/H2 sputter gas mixture with a trace amount of either CS2 or SF6.The spectroscopic technique. Eight rotational transitions of four isotopologues ( Cr Br, Cr Br, Cr Br, and Cr Br) of −1 hollow cathode was located within the resonator cavity of a DCM dye laser operating over the 14,500-16,500 cm range, this radical were recorded in the ground vibrational state, each consisting of fine structure sextets with additional bromine utilizing effective pathlengths of 0.2-1.0 km with the ILS method. The six observed bands are grouped currently into two vi- hyperfine splitting. Spectra were also obtained for the v=1 and v=2 states of 52Cr81Br and 52Cr79Br. The data were fit with brational progressions. The (0,0) bands have been identified by negligible W-isotope shifts, and have red-degraded bandheads a Hund’s case b Hamiltonian and rotational, spin-spin, spin-rotation and hyperfine parameters were determined, including cm−1 cm−1 cm−1 near 15,050 and 15,304 . Both series have a vibrational separation of approximately 525 , and preliminary the higher order spin terms γs and Θ. The hyperfine constants indicate that CrBr has a significant covalent component to its −1 rotational constants of 0.14 cm . These values are consistent with the predicted spectroscopic constants for WS [Sevy et bonding, unlike its chlorine and fluorine counterparts. al., J. Phys. Chem. A, 121, 9446 (2017)], which has not been previously studied experimentally at high resolution. The inclusion of H2 in the sputter gas mixture results in a roughly 10-fold increase in transition intensity. However, this increase in transition intensity is also observed if D2 is added to the sputter gas mixture in place of H2, with no observable rotational WJ09 4:45 – 5:00 or vibrational shift for any of the observed bands. The transitions will be rotationally analyzed and fit using PGOPHER. The FTIR STUDY OF THE REACTIVITY OF TITANIUM ATOMS WITH CARBON MONOXIE AND WATER ISOLATED results of this analysis will be presented. IN SOLID ARGON

MOHAMAD IBRAHIM, PASCALE SOULARD, MONARIS, Sorbonne Universite,´ CNRS, Paris, France; ESMAIL¨ ALIKHANI, MONARIS, Sorbonne Universite,´ Paris, France;BENOITˆ TREMBLAY, MONARIS, Sor- WJ06 3:51 – 4:06 bonne Universite,´ CNRS, Paris, France. PHOTOELECTRON VELOCITY MAP IMAGING SPECTROSCOPY OF BERYLLIUM-CONTAINING TRIATOMIC − ANIONS, BeX2 (X=O,C) Transition metal hydrides are widely used in a variety reactions in chemistry and in particular are important intermediates in catalysis processes such al hydrogenation and hydroformulation. Numerous experimental and theoretical investigations MALLORY THEIS, Department of Chemistry, Emory University, Atlanta, GA, USA;NOAHBJAFFE,Chem- have been focused on the reactions of transition metal atoms and small clusters with H2O or CO. We have studied, in solid istry Department, Emory University, Atlanta, GA, USA; MICHAEL HEAVEN, Department of Chemistry, Emory argon at 12 K, the reactivity of Titanium atoms with a CO+H2O mixture by infrared spectroscopy (FTIR). New infrared peaks University, Atlanta, GA, USA. attributable to the H2COTiO and H2(CO)2TiO complexes were observed in the CO, TiO, and Ti-H2 stretching regions and 13 16 12 18 18 12 16 12 18 in the far infrared. Isotopic substitutions were carried out using C O, C O, H2 O, and a C O+ C O mixture. Beryllium is known to defy conventional bonding motifs in even the smallest of molecular systems. Notable diatomic Characteristic shifts of each isotopologue were identified and used to characterize the geometry of the H2COTiO complex. examples of anomalous bonds include the Be dimer, and dative bonding in BeF− anion. There is a fundamental interest in understanding how beryllium’s bonding characteristics develop with increasing molecular complexity. In the past year, − − we have moved forward with studies of triatomic species, specifically BeO2 and BeC2 , through a combination of photo- WJ10 5:03 – 5:18 electron velocity map imaging spectroscopy and ab initio computational methods. In this talk, we will present our current MATI SPECTROSCOPY OF Ln(OH)2 (Ln = La AND Ce) FORMED BY O-H BOND ACTIVATION OF WATER. understanding of the bonding in these molecules, with comparisons to previously characterized diatomic molecules (BeO−, − − BeS ,BeF ). SILVER NYAMBO, JONG HYUN KIM, PRIYA KARNA, YUCHEN ZHANG, DONG-SHENG YANG, De- partment of Chemistry, University of Kentucky, Lexington, KY, USA.

WJ07 4:09 – 4:24 Lanthanide (Ln = La and Ce) atom reactions with water are carried out in a pulsed-laser ablation molecular beam source 1 and characterized by mass-analyzed threshold ionization (MATI) spectroscopy and quantum chemical calculations. Both re- FOURIER TRANSFORM MICROWAVE SPECTROSCOPY OF LiNH2 and NaNH2 (X˜ A1): COMPARING actions yield Ln(OH)2 as the main product through a hydrogen atom elimination of each water molecule. The MATI spectra QUADRUPOLE HYPERFINE INTERACTIONS of Ln(OH)2 are dominated by the origin band and metal-ligand symmetric stretching and bending vibronic progressions. Adi- −1 −1 abatic ionization energies measured from the spectra are 40135 (5) cm for La(OH)2 and 40756 (5) cm for the Ce(OH)2. MARK BURTON, Department of Chemistry and Biochemistry, University of Arizona, Tucson, AZ, USA;BEN- 1 2 2 3 The molecular symmetry of Ln(OH)2 is C2v, and the observed transitions are A1 - A1 for La(OH)2 and B1 - B1 for JAMIN RUSS, PHILLIP M. SHERIDAN, Department of Chemistry and Biochemistry, Canisius College, Buffalo, 1 1 1 Ce(OH)2. The ground valence electron configurations of La(OH)2 and Ce(OH)2 are La 6s and Ce 4f 6s , respectively. NY, USA;LUCYM.ZIURYS,Department of Chemistry and Biochemistry, Department of Astronomy, The Uni- Ionization of each species removes a Ln 6s-based electron, and the resultant ion also has C2 symmetry. The spectrum of versity of Arizona, Tucson, AZ, USA. v Ce(OH)2 has a broader linewidth than that of La(OH)2, which is attributed to the unresolved spin-orbit levels by comparing 1 Rotational spectra of LiNH2 and NaNH2 in their X˜ A1 ground electronic states have been recorded using pulsed-beam with relativistic quantum calculations at the level of spin-orbit multi-reference quasi-degenerated perturbation theory. The Fourier transform spectroscopy in the frequency range 22-58 GHz. These species were synthesized in a DC discharge by the metal-mediated hydrogen elimination of water is predicted to be thermodynamically and kinetically favorable by the density reaction of ammonia and the respective laser-ablated alkali metal, in argon carrier gas. Observed transitions were analyzed functional theory calculations. with previously-measured millimeter-wave frequencies, improving previous rotational constants and determining the metal electric quadrupole hyperfine parameter, χaa, for both species. We find that χaa (Li) = 0.494 and χaa (Na) = -7.688. We also compare our results to DFT calculations. A Townes-Dailey analysis of the quadrupole constants suggest that the bonding of the –NH2 ligand to lithium and sodium is comparable. 176 177 WK. Mini-symposium: High-Harmonic Generation and XUV Spectroscopy WK03 2:39 – 2:54 Wednesday, June 19, 2019 – 1:45 PM THE ROLE OF LATTICE DEFECTS ON THE ELECTRON DYNAMICS AND PHOTOCHEMISTRY OF CuFeO2 DE- Room: B102 Chemical and Life Sciences LAFOSSITE Chair: Robert Baker, The Ohio State University, Columbus, OH, USA ELIZABETH A FUGATE, SOMNATH BISWAS, YUTICHAI MUEANNGERN, MATHEW CLEMENT, De- partment of Chemistry and Biochemistry, The Ohio State University, Columbus, OH, USA; MINKYU KIM, DONGJOON KIM, ARAVIND ASTHAGIRI, Department of Chemical and Biochemical Engineering, The Ohio State University, Columbus, OH, USA;ROBERTBAKER,Department of Chemistry and Biochemistry, The Ohio State University, Columbus, OH, USA.

Metal oxides are stable, earth abundant semiconductors for the photochemical conversion of sunlight into chemical energy. Delafossite CuFeO2 is a promising material for photochemical energy conversion due to its small band gap (1.5 eV) and p-type conductivity. CuFeO2 has also shown promise for catalyzing both the hydrogen evolution and CO2 reduction WK01 INVITED TALK 1:45 – 2:15 reactions. Despite significant work in this area, important questions remain regarding the complex defect chemistry in copper- ULTRAFAST XUV SPECTROSCOPY TO PROBE CONICAL INTERSECTIONS AND EXCITED STATE DYNAMICS iron oxides and the effect of various defects on the carrier lifetime and photoelectrochemical efficiency. Of the various defects possible, here we investigate the role of type II heterojunction structures with interfaces of CuO and CuFeO2, Cu ARVINDER SANDHU, Department of Physics, University of Arizona, Tucson, AZ, USA. vacancies, and O interstitials on the photocarrier dynamics of this material. To elucidate the effects of carrier lifetimes on the photochemical efficiency of mixed phase CuFeO2, we probe the photocarrier dynamics using optical transient absorption Femtosecond and attosecond XUV spectroscopy was used to study of electron dynamics stemming spectroscopy. First, we consider the role of grain boundaries between CuO and CuFeO2 in mixed phase systems, which from many-body interactions, including the coupling between the electronic and nuclear degrees of free- have been hypothesized to facilitate charge separation across this type II heterostructure. Transient absorption measurements a dom, electronic correlations, external light fields, or a combination thereof. suggest that photoexcited electrons in the most active materials reside on Fe 3d conduction band states, and we do not observe Conical intersections are an important topic of investigation because they serve as nature’s energy evidence for electron transfer to CuO, which indicates interfacial charge transfer from CuFeO2 to CuO is not responsible funnels in many biochemical processes, e.g. vision, light harvesting, etc. We focused on nuclear motion for enhanced carrier lifetimes in the catalysts studied here. We find that Cu vacancies appear to improve the efficiency of mediated evolution of an electron hole near a conical intersection in a CO2 ion. Using pump-probe pho- CuFeO2 due to fast charge separation as holes thermalize from O 2p to Cu 3d valence band states. This is confirmed by todissociation spectroscopy, we made quantitative measurements of electronic couplings and monitored DFT calculations demonstrating a lowering of the Cu 3d band center with the introduction of Cu vacancies. In contrast, DFT the role of decoherence in such dynamics, thereby probing the fundamental mechanisms responsible for calculations show that the valence band maximum of CuFeO2 changes from Cu 3d to O 2p states with the introduction of the charge and energy redistribution in molecules. interstitial O atoms which tends to inhibit charge separation. Based on our results as well as DFT calculations, we conclude In another study, time resolved XUV photoelectron spectroscopy was applied to identify the role of multi electron exci- that Cu vacancies are primarily responsible for charge separation in this material. tations in the ultrafast Rydberg state dissociation of highly excited states in O2. The talk will also discuss new opportunities arising the application of attosecond soft-x-ray sources.

aThis work was supported by the U. S. Army Research Laboratory and the U. S. Army Research Office under grant number W911NF-14-1-0383 and the National Science Foundation (NSF) award number PHY-1505556.

WK04 2:57 – 3:12 TOWARDS EXTREME ULTRAVIOLET TIME-RESOLVED LIQUID PHOTOELECTRON SPECTROSCOPY UTILIZ- ING A HIGH-HARMONIC GENERATION PROBE SOURCE

ZACHARY N. HEIM, BLAKE A ERICKSON, ERICA LIU, DANIEL NEUMARK, Department of Chemistry, The University of California, Berkeley, CA, USA. WK02 2:21 – 2:36 THE ELECTRONIC PROPERTIES OF 2D-TaS2 BASED PHOTOCATALYTIC MATERIALS INVESTIGATED BY FS- Time-resolved photoelectron spectroscopy (TRPES) has been used to study the ultrafast relaxation of electronically XUV PHOTOEMISSION SPECTROSCOPY excited thymine, thymidine, and thymidine monophosphate on femtosecond time scales in liquid water. Pump-probe ex- periments have been carried out using tunable UV (4.7-5.2 eV) and 200 nm (6.2 eV) pulses, enabling the observation of 1 1 MIHAI E VAIDA, Department of Physics, University of Central Florida , Orlando, FL, USA. relaxation dynamics of excited state populations from the S1( ππ*) excited state as well as a higher lying Sn( ππ*) excited 1 a state. Relaxation lifetimes from the S1( ππ*) excited state have been obtained in reasonable agreement with previous work 1 b c Anthropogenic CO2 has become an important global issue due to its increasing atmospheric levels. Therefore, catalytic and show no evidence of relaxation to the S2( nπ*) excited state, in contrast to transient absorption studies. , Additionally, 1 and photocatalytic materials that can be used to transform CO2 into valuable chemicals are of high prominence. Temperature relaxation from the higher lying Sn( ππ*) excited state populated at 200 nm (6.2 eV) has been measured by TRPES for the programed desorption and reaction experiments performed in our laboratory demonstrate that defect rich two dimensional first time and found to have a sub-picosecond lifetime. The current liquid TRPES experiment is unable to observe ground (2D) TaS2 is a remarkable CO2 activator. Therefore, in this work 2D-TaS2 nanoflakes and layers, which have a metallic state population recovery subsequent to photoexcitation of these nucleic acid constituents due to insufficient probe energies. character are investigated as potential co-catalysts for highly efficient photocatalytic materials that facilitate the CO2 reduc- To remedy this deficiency, we are working to implement high-harmonic generation as a source of femtosecond XUV pulses tion reaction. 2D-TaS2 is synthesized on semiconductor substrates such as 2D-MoS2 and Si(111) under ultrahigh vacuum capable of photoionizing solvated species with larger binding energies. conditions by evaporating Ta atoms in an H2S atmosphere. The composition and the crystallinity of the 2D-TaS2 are inves- aBuchner, F.; Nakayama, A.; Yamazaki, S., et al., Journal of the American Chemical Society 2015, 137 (8), 2931-2938. tigated by Auger electron spectroscopy and low energy electron diffraction. The electronic properties of TaS2 are analyzed bHare, P. M.; Crespo-Hernandez,´ C. E.; Kohler, B., Proceedings of the National Academy of Sciences 2007, 104 (2), 435-440. via femtosecond extreme ultraviolet photoemission spectroscopy by monitoring the valence electrons as the size of TaS2 is cKwok, W.-M.; Ma, C.; Phillips, D. L., Journal of the American Chemical Society 2008, 130 (15), 5131-5139. increase form small particles to nanoflakes to extended 2D layers.

Intermission 178 179

WK05 3:51 – 4:06 WK07 4:27 – 4:42 DEVELOPMENT OF SOLUTION-PHASE XUV ABSORPTION SPECTROSCOPY USING FEMTOSECOND TABLETOP XUV SPECTROSCOPY TO STUDY NICKEL CATALYSIS

KORI SYE, Chemistry, University of Illinois at Urbana-Champaign, URBANA-CHAMPAIGN, IL, USA;JOSH KRISTOPHER BENKE, JOSH VURA-WEIS, Department of Chemistry, University of Illinois at Urbana- VURA-WEIS, Department of Chemistry, University of Illinois at Urbana-Champaign, Urbana, IL, USA. Champaign, Urbana, IL, USA.

Ultrafast extreme ultraviolet (XUV) absorption spectroscopy can be used to probe the dynamics of excited states in first- To improve the efficiency of first row transition metal catalysts to match their precious metal counterparts, a method row transition metals complexes with sensitivity to the oxidation state, spin state, and ligand field of the metal center. This must be used that can look at snapshots of the catalytic reaction and identify the salient qualities of key intermediates. technique can be performed with a tabletop instrument and probes the M-edge transitions from the 3p to the 3d orbital of Ultrafast tabletop extreme ultraviolet (XUV) spectroscopy is well suited to this purpose because it is sensitive to a metal’s a metal center. This technique is analogous to K-, and L-edge spectroscopy, which are performed at synchrotron or x-ray oxidation state, spin state, and ligand field. In addition, it can be performed in the lab rather than at a largescale facility free electron lasers. These user-based facilities offer high photon counts and ultrafast time resolution, however beamtime like a synchrotron or X-FEL. To demonstrate sensitivity of XUV spectroscopy to the electronic structure of nickel-centered is limited. Fortunately, the use of tabletop sources to generate XUV light with femtosecond time resolution has become a complexes, I measure the photophysics of a nickel dithiocarbamate complex, nickel bis(diethyldithiocarbamate), chosen due more widely available source of x-ray spectroscopy. XUV absorption spectroscopy has until now been limited to studying to its similarities to catalytically-active nickel dithiolenes. I show how the electron density moves across the highly covalent solid-state or gas-phase samples due to short penetration depth of XUV photons. To study solutions with XUV absorption, I nickel-sulfur bonds after excitation of an LMCT transition. Examining the excited state dynamics with XUV spectroscopy used a microfluidic chip to generate free flowing liquid sheets of nonpolar, XUV transmissive solutions. I have characterized allows for clearer determination of the metal spin state and electron density, filling in gaps in the picture drawn by transient the thickness and stability of chloroform liquid sheets under vacuum and have adapted our tabletop high-harmonic instrument optical spectroscopy. Transient XUV spectroscopy is shown to measure both the electronic structure of the metal and the to maintain high vacuum. This sample delivery method now makes ultrafast XUV absorption spectroscopy available to study electron density on the ligand, providing a powerful tool to study charge flow between metal and ligand. an array of transition-metal complexes in the solution phase.

WK06 4:09 – 4:24 CONTROLLING PHOTOEXCITED STATE DYNAMICS AT HEMATITE SURFACES

SAVINI SANDUNIKA BANDARANAYAKE, SOMNATH BISWAS, ROBERT BAKER, SPENCER WAL- LENTINE, Department of Chemistry and Biochemistry, The Ohio State University, Columbus, OH, USA.

Hematite is an earth abundant material that has the potential to be used as a photoanode for oxygen evolution from water using solar energy. Modifications such as surface functionalization, surface doping, use of a co-catalyst and preparation of layered heterojunctions have each been explored in an effort to increase the efficiency of the hematite electrode with varying degrees of success. However, due to the complexity of this material and the challenges associated with probing electron and hole dynamics with surface specificity and chemical state resolution, the fundamental processes governing carrier transport and trapping in surface states is still not well understood. In particular, recent transient studies carried out on hematite using extreme ultraviolet (XUV) absorption spectroscopy and XUV reflection absorption (RA) spectroscopy show key differences in the dynamics of small polaron formation in bulk hematite versus at the surface. To better understand the origin of these differences, we have functionalized hematite surfaces with a series of small organic molecules, including phenyl phosphonic acid (PPA), 4-Cyano PPA and 4-methoxy PPA. These molecularly functionalized surfaces have been characterized using x-ray photoelectron spectroscopy and sum frequency generation vibrational spectroscopy. Linear sweep voltammetry measurements is used to explore the effect of these systematic surface modifications on the photoelectrochemical efficiency of this material. To better understand the mechanism by which surface modification influences catalytic efficiency, transient XUV-RA spectroscopy is used to measure changes in the rate of small polaron formation and surface trapping in these materials. This direct observation of electron and hole dynamics in systematically modified hematite surfaces provides a better understanding of the material properties responsible for mediating energy conversion efficiency in these and related materials. 180 181 WL. Spectroscopy as an analytical tool Wednesday, June 19, 2019 – 1:45 PM WL03 2:21 – 2:36 Room: 2079 Natural History QUANTITATIVE DETERMINATION OF ENANTIOMERIC EXCESS BY MICROWAVE THREE-WAVE MIXING Chair: Jessie P Porterfield, Harvard Smithsonian Ctr for Astrophysics, Cambridge, MA, USA MARTIN S. HOLDREN, BROOKS PATE, TAYLOR SMART, ARTHUR WU, Department of Chemistry, The University of Virginia, Charlottesville, VA, USA.

WL01 1:45 – 2:00 Microwave three-wave mixing is a rotational spectroscopy technique that can measure the difference between a pair or DETERMINATION OF ENANTIOMERIC EXCESS IN THE HIGH ENANTIOPURITY LIMIT USING CHIRAL TAG- enantiomers and quantify a ratio between them where traditional rotational spectroscopy cannot. The measurement principle GING ROTATIONAL SPECTROSCOPY was shown in 2013 by Patterson, Schnell, and Doyle using a DC field to achieve the necessary state mixing [1] and was extended by Patterson and Doyle later that year to the three-wave mixing approach most commonly used now [2]. Grabow, KEVIN J MAYER, BROOKS PATE, CHANNING WEST, REILLY E. SONSTROM, MARTIN S. HOLDREN, also in 2013, has provided a description of the measurement in the intuitive language of NMR spectroscopy [3]. Despite TAYLOR SMART, Department of Chemistry, The University of Virginia, Charlottesville, VA, USA;LUCA the introduction of the technique in 2013, there has been little work to develop the method into a quantitative analytical EVANGELISTI, Dep. Chemistry ’Giacomo Ciamician’, University of Bologna, Bologna, Italy. chemistry tool. In this talk we focus on using this method for enantiomeric excess (EE) determinations. Because the chiral signal produced in this technique is proportional to the difference in the enantiomer populations (a value that is proportional Chiral tag rotational spectroscopy can be used for quantitative determination of the ratio of the two enantiomers of a chiral to the total amount of sample present), it is necessary to reference the amplitude of the chiral signal to a quantity proportional molecule. The strategy for chiral tag rotational spectroscopy is to convert the enantiomers of the analyte into diastereomers to the total sample concentration – available from a “normal” rotational signal measurement. Furthermore, the method through non-covalent attachment of a small, chiral tag molecule. The analyte enantiomer ratio, which is used to determine the requires a sample of known EE for scale calibration – a significant limitation in analytical chemistry. The results from two enantiomeric excess (EE), is determined by comparing the transition intensities of rotational transitions for the homochiral measurement pulse sequences that provides total population calibration will be presented. Calibration curves for samples that and heterochiral complexes when both a racemic and enantiopure tag sample is used. A calibration curve for EE determination cover a range of EE (gravimetrically calibrated) will be presented for isopulegol and menthone. The ability to obtain accurate of 3-methylcyclohexanone tagged with 3-butyn-2-ol will be presented. The role that intensity fluctuations in back-to-back EE determinations in a simple mixture using the calibrated measurement scheme is tested using two commercial samples measurements of the rotational spectra of the chiral tag complexes play in determining the EE measurement accuracy will of isopulegol that contain all eight stereoisomers produced in the citronellal cyclization reaction. The three-wave mixing be described. In applications to pharmaceutical chemistry the main need is the ability make quantitative EE determinations technique can provide EE accuracy to about 5%, and this performance, especially for high enantiopurity samples, limits its in the high enantiopurity limit of the analyte. This requirement poses challenges for chiral tag rotational spectroscopy from applicability in many industry applications. both the measurement sensitivity and the availability of high enantiopurity tag samples. Two analysis methods for high EE [1] D. Patterson, M. Schnell, and J.M Doyle, “Enantiomer-specific detection of chiral molecules via microwave spec- measurements will be discussed. In one case, the enantioimpurity detection limit is decreased by the co-adding of multiple troscopy”, Nature 497, 475- 478 (2013). [2] D. Patterson and J.M. Doyle, “Sensitive Chiral Analysis via Microwave Three- rotational transitions of the homochiral and heterochiral tag complex. The second strategy uses a lower enantioimpurity tag Wave Mixing”, Phys. Rev. Lett. 111, 023008 (2013). [3] J. Grabow, “Fourier Transform Microwave Spectroscopy: Handed- to speed the EE determination of high enantioimpurity samples. In this case, the ability to accurately determine the tag EE is ness Caught by Rotational Coherence”, Angew. Chem. Int. Ed. 52, 11698-11700 (2013). crucial and the functional dependence of EE measurement precision in chiral tag rotational spectroscopy provides the limit on measurement accuracy that can be achieved. WL04 2:39 – 2:54 PERFORMANCE OF THREE-WAVE MIXING ROTATIONAL SPECTROSCOPY FOR THE DETERMINATION OF WL02 2:03 – 2:18 ENANTIOMERIC EXCESS IN COMPLEX CHEMICAL MIXTURES CALIBRATING THE ENANTIOMERIC EXCESS OF CHIRAL TAGS TO IMPROVE MEASUREMENT ACCURACY USING A SIMPLIFIED 6-18 GHZ CHIRPED-PULSE FOURIER TRANSFORM MICROWAVE SPECTROMETER TAYLOR SMART, BROOKS PATE, MARTIN S. HOLDREN, ARTHUR WU, Department of Chemistry, The University of Virginia, Charlottesville, VA, USA. CHANNING WEST, Department of Chemistry, The University of Virginia, Charlottesville, VA, USA;LUCA EVANGELISTI, Dipartimento di Chimica G. Ciamician, Universita` di Bologna, Bologna, Italy;REILLYE. The method of microwave three-wave mixing can be used to perform chiral analysis by molecular rotational SONSTROM, BROOKS PATE, Department of Chemistry, The University of Virginia, Charlottesville, VA, USA. spectroscopy.[1-3] We have developed pulse sequences that can be used to determine the enantiomeric excess (EE) of a component that is present in a complex mixture. To make an EE determination, the measurement needs both a chiral three- The enantiomeric excess (EE) of a chiral sample can be determined from molecular clusters of the analyte and a chiral wave mixing measurement and a signal that is proportional to the total amount of the molecules. The measurement provides tag in a pulsed-jet expansion. The complexation converts analyte enantiomers into rotationally distinct diastereomer com- both the EE and the identity of the dominant enantiomer (Based on the phase). Furthermore, a sample of known EE must plexes. The EE is determined by comparing rotational transition intensities resulting from diastereomer complexes when a be available to generate a calibration curve. Validation measurements of the technique indicate that EE determinations with racemic tag is used and when an enantiopure tag is used. For a pair of diastereomer transitions, the connection between the about 5% accuracy are possible using this technique. The major strength of three-wave mixing is its ability to perform normalized intensity ratio (R) and the analyte EE is: (R-1)/(R+1) = (EEanalyte)(EEtag). Therefore, accurately determining EE measurements directly in complex mixtures. Unlike chiral tag rotational spectroscopy, three-wave mixing does not add an analyte EE requires an accurate “enantiopure” tag EE. The EE calibration of three frequently used tags (3-butyn-2-ol, to spectral congestion resulting from the formation of isomers with the chiral tag. The performance of the calibrated EE propylene oxide, and 2-(trifluoromethyl)oxirane) is described. For butynol, EE determinations are possible using homochi- schemes presented previously at ISMS [4] and expanded in the previous talk will be presented for EE determinations of ral and heterochiral dimers, known as “auto tagging.” Optimal sensitivity is achieved between 6-18 GHz due to the size of molecular components in essential oils. Primary validation comes from spiking a new chiral molecule with known EE into an the dimers. A pulse generation system utilizing a frequency doubler with low harmonic generation is employed to improve essential oil. EE determinations of menthone and isomenthone in a series of commercial samples that have also been analyzed spurious signal performance compared to schemes requiring an external reference clock. Several butynol dimer isomers are by the chiral tag method will be reported. These measurements show that both menthone and isomenthone are found in high formed in the jet expansion, and EE determinations are equivalent regardless of the isomers used in the analysis. Determi- enantiopurity in natural samples. nation of EE by auto tagging was validated by chiral GC. Also, a series of butynol samples with EE between 50 and 90 [1] D. Patterson, M. Schnell, and J.M Doyle, “Enantiomer-specific detection of chiral molecules via microwave spec- were prepared gravimetrically by mixing high enantiopurity butynol (EE = 98% by chiral GC and auto tag) with racemic troscopy”, Nature 497, 475- 478 (2013). [2] D. Patterson and J.M. Doyle, “Sensitive Chiral Analysis via Microwave Three- butynol. Chiral tagging measured the EEs in this range with greater accuracy than chiral GC. The EEs of propylene oxide Wave Mixing”, Phys. Rev. Lett. 111, 023008 (2013). [3]J. Grabow, “Fourier Transform Microwave Spectroscopy: Hand- and 2-(trifluoromethyl)oxirane were determined by tagging with the calibrated butynol. Neither molecule reports an EE in edness Caught by Rotational Coherence”, Angew. Chem. Int. Ed. 52, 11698-11700 (2013). [4] M.S. Holdren, B. Pate, C. their Certificate of Analysis, possibly because their high volatility precludes separation by chiral GC. To validate the EE Embly, A. Wu, K.J. Mayer, J. Dittman, P. Buonicotti, G. Haghtalab, B. Mitchell, “Enantiomeric Excess Measurements using determinations, both tags were used to measure the EE of an analyte and were found to be equivalent within measurement Microwave Three-Wave Mixing”, Talk TC08, ISMS 73rd Meeting Archive, https://dx.doi.org/10.15278/isms.2018.TC08. accuracy. Intermission 182 183

WL05 3:33 – 3:48 WL07 4:09 – 4:24 CHIRAL ANALYSIS OF THUJONE IN ESSENTIAL OIL SAMPLES PROGRESS ON THE DEVELOPMENT OF A MILLIMETER-WAVE CHIRALITY SPECTROMETER (CHIRALSPEC)

REILLY E. SONSTROM, KEVIN J MAYER, CHANNING WEST, BROOKS PATE, Department of Chemistry, MARTIN S. HOLDREN, DEACON J NEMCHICK, JOHN PEARSON, SHANSHAN YU, Jet Propulsion Lab- The University of Virginia, Charlottesville, VA, USA. oratory, California Institute of Technology, Pasadena, CA, USA; BROOKS PATE, Department of Chemistry, The University of Virginia, Charlottesville, VA, USA. Thujone is a natural product present in several common plants, such as sage, cedar leaf, and wormwood.[1] Thujone is a neurotoxin that can cause serious health complications in high concentrations, with different stereoisomers having different Homochirality is omnipresent in nature on Earth in which life predominately utilizes one handedness of a chiral molecule levels of toxicity.[1] This work extends on previous work to analyze thujone by molecular spectroscopy,[2-3] and presents over another. It is considered a biomarker that can aid in the search for life elsewhere in the solar system on places like Mars, new efforts to determine the enantiomeric excess (ee) of the alpha- and beta-thujone in several essential oil (EO) samples Titan, Europa, and Enceladus. The 2013 planetary science Decadal Survey recommends “a detailed characterization of organ- by chiral tagging. There are four stereoisomers of thujone which arise from the different orientation of the methyl and ics to search for signatures of biological origin, such as molecules with preferred chirality or unusual patterns of molecular isopropyl group on the bicyclo[3,1,0]hexan-3-one structure. Alpha-thujone has the methyl and isopropyl group trans and weights” as a key future investigation for determining the possibility of life beyond Earth. Mass spectrometers are the primary beta-thujone has the two groups cis. Each of these diastereomers have three conformers from the rotational of the isopropyl choice for chemical detection and identification of simple organics for planetary and astrobiology investigations. However, group. Of the three conformers, all three of alpha-thujone and the lowest two of beta-thujone were observed experimentally. mass spectrometry alone cannot address the challenge of successfully deconvolving mixtures of structurally complex organic In order to determine the enantiomeric excess of alpha- and beta-thujone in various samples, the homochiral and heterochiral molecules of approximately the same molecular weight; this includes lacking the chirality detection capability required for complexes with propylene oxide were assigned using quantum chemistry calculations at the B3LYP D3BJ / def2tzvp level of analysis of chiral molecules. theory. There was 13C-level sensitivity to determine carbon framework structures of the strongest homochiral and heterochiral ChiralSpec can provide synergetic measurements to mass spectrometers for planetary science and is funded by the NASA complex of alpha-thujone. Several sage and cedar leaf essential oils were analyzed. There was high enantiopurity of alpha- Planetary Instrument Concept for the Advancement of Solar System Observations (PICASSO) program. ChiralSpec is a and beta-thujone in all samples. Additionally, we were able to determine the ee of fenchone, which is present in in cedar leaf millimeter-wave spectrometer operated in two modes: (1) chirality detection mode, based on a novel three-wave mixing; and EO samples, and camphor, which is present in opposite enantiopurity in sage and cedar leaf.[4] (2) survey mode, with the instrument acting as a traditional millimeter-wave spectrometer to characterize chemical composi- [1] Williams, J. D. et al. (2016). Detection of the Previously Unobserved Stereoisomers of Thujone in the Es- tion and quantify abundance of planetary samples. ChiralSpec extends the work done on microwave three-wave mixing into sential Oil and Consumable Products of Sage (Salvia officinalis L.) Using Headspace Solid-Phase Microextraction-Gas higher frequencies of light where size, weight, and power of many components of the instrument can be reduced. Chromatography-Mass Spectrometry. Journal of Agricultural and Food Chemistry, 64(21), 4319-4326. [2] Kisiel, Z.; We will report on the current state of this instrument and its future developments. G-band (180-200GHz) and W-band Legon, A.C. (1978). Conformations of Some Bicyclic Monoterpenes Based on Bicyclo[3.1.0]hexane from Their Low- (70-90GHz) excitation channels have been designed, tested, and optimized to show that power requirements are met and that Resolution Microwave Spectra. Journal of the American Chemical Society, 100, 8166-8169. [3] Kisiel, Z. Chirped molecular emission can be detected for many two level systems for a test case molecule, propylene oxide. Three-wave mixing pulse rotational spectroscopy of a single thujone+water sample. In International Symposium of Molecular Spectroscopy, experiments are on-going, and we will report our findings. http://hdl.handle.net/2142/91165: 2016. [4] Tateo, F. et al. (1999). Update on enantiomeric composition of (1R)-(+)- and (1S)-(-)-camphor in essential oils by enantioselective gas chromatography. Anal. Commun., 36, 149-151.

WL08 4:27 – 4:42 STEREOCHEMICAL IDENTIFICATION OF AN INTERMEDIATE IN THE SYNTHESIS OF DOLUTEGRAVIR USING WL06 3:51 – 4:06 MOLECULAR ROTATIONAL RESONANCE SPECTROSCOPY MOLECULAR SIZE LIMITS FOR ROTATIONAL SPECTROSCOPY AND THE HIGH-J LIMIT OF THE RIGID ROTOR JUSTIN L. NEILL, MATT MUCKLE, BrightSpec Labs, BrightSpec, Inc., Charlottesville, VA, USA;LUCA BROOKS PATE, Department of Chemistry, The University of Virginia, Charlottesville, VA, USA; LUCA EVAN- EVANGELISTI, Dipartimento di Chimica G. Ciamician, Universita` di Bologna, Bologna, Italy; REILLY E. GELISTI, Dipartimento di Chimica G. Ciamician, Universita` di Bologna, Bologna, Italy; JUSTIN L. NEILL, SONSTROM, BROOKS PATE, Department of Chemistry, The University of Virginia, Charlottesville, VA, USA; BrightSpec Labs, BrightSpec, Inc., Charlottesville, VA, USA; CHANNING WEST, Department of Chemistry, JO-ANN JEE, B FRANK GUPTON, THOMAS D. ROPER, Chemical and Life Science Engineering, Virginia The University of Virginia, Charlottesville, VA, USA. Commonwealth University, Richmond, VA, USA.

Molecular rotational spectroscopy is well suited for the analysis of regioisomers, which has applications in pharmaceu- Over half of pharmaceuticals, both among the top 100 drugs by prescription totals and new U.S. Food and Drug Admin- tical synthesis. Rotational spectroscopy offers important advantages over other chemical analysis techniques resulting from istration (FDA) approvals, contain at least one chiral center. Moreover, most new chiral pharmaceuticals are synthesized as extreme sensitivity to molecular mass distribution, high accuracy molecular structure (and, therefore, rotational constant) a single isomer. Therefore, it is important to be able to determine the primary isomer generated by a synthetic process as predictions from quantum calculations, and the combination of high-spectral resolution and dynamic range. The sensitivity well as the presence of any other isomers - preferably directly on the intermediate compounds where each chiral center has and range of the technique allow low abundance regioisomer impurities to be quantitatively measured without chemical sep- been introduced. Molecular rotational spectroscopy, with its sensitivity to small changes in structure and ability to identify aration. The challenge for rotational spectroscopy is that actual measurement challenges in pharmaceutical chemistry involve compounds directly from electronic structure theory, can be a powerful tool in this application. molecules in the 200-500 Da mass range. Unique features of the rotational kinetic energy levels lead to decreasing peak The present study concerns dolutegravir, an HIV integrase inhibitor developed by GlaxoSmithKline and approved by the FDA in 2013. Efforts are ongoing at the Medicines for All institute in Richmond, Virginia to develop a stereoselective flow transition strength as the molecular size increases as well as a decrease in the frequency where the strongest transitions occur. a However, special features of the high-J limit (semiclassical limit) of the rigid rotor Hamiltonian potentially mitigate these synthesis for dolutegravir to reduce its cost and increase availability. As part of a new route development, an intermediate experimental difficulties and suggest that rotational spectroscopy can be applied to much larger molecules than previously ex- with two chiral centers was assessed by rotational spectroscopy to determine which diastereomer was the predominant one pected. The rotational spectra of a series of high vapor pressure large molecules in both the limiting prolate and oblate limits formed by the process. Notably, NMR was unable to conclusively determine this, but rotational spectroscopy unambiguously are analyzed. For the prospect of analyzing larger molecules, the prolate limit appears to offer major advantages. However, determined that the synthetic route produced the correct stereochemistry. This result suggests that rotational spectroscopy can experiments using pulsed-jet sources show rapid relaxation of these high-energy rotational levels and, at present, appear to be a useful complement to other analytical characterization methods in organic process development. reduce the major advantages suggested by the rotational spectroscopy in the high-J limit. aR.E. Ziegler, B.K. Desai, J.-A. Jee, B.F. Gupton, T.D. Roper, and T.F. Jamison, Angew.Chem.Int.Ed., 2018, 130, 7299-7303. 184 185 RA. Plenary WL09 4:45 – 5:00 Thursday, June 20, 2019 – 8:30 AM TERAHERTZ ANALYTICAL CHEMICAL SENSING OF EXPIRED HUMAN BREATH. Room: Foellinger Auditorium DANIEL J TYREE, HANNAH N BENSTON, Department of Physics, Wright State University, Dayton, OH, Chair: Anthony Remijan, NRAO, Charlottesville, VA, USA USA; PARKER K HUNTINGTON, Department of Physics, MIT, Cambridge, MA, USA; BRENT D FOY, IVAN MEDVEDEV, Department of Physics, Wright State University, Dayton, OH, USA.

We report on our recent research on applying Terahertz molecular sensing to quantitative analysis of human breath. A recently developed tabletop THz gas sensor has been demonstrated to detect a range of breath volatiles at a part per billion/trillion level of dilution. In a recent project we developed several statistical models of fatigue based on THz analyses RA01 8:30 – 9:10 of expired human breath. Breath of ten subjects was sampled over the course of a 40-hour sleep deprivation study performed CURRENT AND FUTURE PROSPECTS, AS WELL AS CHALLENGES FOR ALMA MOLECULAR LINE STUDIES by Navy Medical Research Unit – Dayton (NAMRU-D) at Wright Patterson Air Force Base. The breath-fatigue models presented here predict the reaction times measured by Psychomotor Vigilance Task test along the timeline of sleep deprivation CRYSTAL L. BROGAN, NAASC, National Radio Astronomy Observatory, Charlottesville, VA, USA. study. This promising application of THz gas sensing hold a lot of potential for a range of civilian and military applications. In this talk I will cover three topics. First, I will present some recent highlights from ALMA related to astrochemistry. Second, I will describe some of the challenges inherent in analyzing ALMA spectroscopic data, using as an illustrative WL10 5:03 – 5:18 template observations of NGC6334I - a cluster of forming massive protostars. Finally, I will give an overview of approved TERAHERTZ SPECTROSCOPIC MOLECULAR SENSOR FOR QUANTITATIVE ANALYTICAL GAS SENSING and future ALMA development projects that promise to open new windows for molecular spectroscopic study with ALMA. DANIEL J TYREE, Department of Physics, Wright State University, Dayton, OH, USA; PARKER K HUNTING- TON, Department of Physics, MIT, Cambridge, MA, USA; ROBERT M SCHUELER, Department of Physics, Wright State University, Dayton, OH, USA; JENNIFER HOLT, CHRISTOPHER F. NEESE, Department of Physics, The Ohio State University, Columbus, OH, USA;IVANMEDVEDEV,Department of Physics, Wright State University, Dayton, OH, USA. RA02 9:15 – 9:55 MOLECULAR SPECTROSCOPY AT THE JET PROPULSION LABORATORY Quantitative analytical gas sampling is of great importance in a range of environmental, safety, and scientific application. In this article we present the design, operation, and performance of a recently developed table top Terahertz spectroscopic BRIAN DROUIN, Jet Propulsion Laboratory, California Institute of Technology, Pasadena, CA, USA. molecular sensor capable of rapid (minutes) and sensitive (part per trillion level of dilution) detection of a wide range of gaseous analytes with ‘absolute’ specificity. The technique presented in this paper excels at detecting light polar volatile Quantitative spectrometry is a primary source for determination of composition as well as physical properties of plan- compounds which often challenge the capabilities of competing gas sensing techniques. etary atmospheres, including the Earth’s and exo-planetary atmospheres. NASAs charter to explore the universe, the solar system, and to observe Earth from space results in several different challenges for molecular spectroscopy, including: (1) a desire for comprehensive spectral databases; (2) extreme physical characterizations of bulk atmospheric gases; (3) character- ization of transient molecules; (4) development of sensors for extraterrestrial deployment. Along with colleagues across the world, the molecular spectroscopy laboratory at NASAs Jet Propulsion Laboratory works towards these goals, providing both critical information for specific missions as well as general knowledge to support a broad community of planetary scientists, astronomers, and Earth scientists. This presentation will show examples in each challenging area with highlights for spectral characterization efforts to support the Herschel/HIFI and Cassini missions, high-pressure spectroscopy to support the OCO missions and exoplanet research, characterizations of radical and ion species, as well as the development of miniaturized cavity spectrometers that may enable molecular and enantiomeric specific detections in-situ.

Intermission

RAO AWARDS 10:35 Presentation of Awards by Jennifer van Wijngaarden, University of Manitoba

2018 Rao Award Winners Zaijun Chen, Max Planck Institute of Quantum Optics Elijah Jans, The Ohio State University Elizabeth Ryland, University of Illinois at Urbana-Champaign

MILLER PRIZE 10:45 Introduction by Michael Heaven, Emory University 186 187 RG. Mini-symposium: Astrochemistry and Astrobiology in the age of ALMA RA03 Miller Prize Lecture 10:50 – 11:05 Thursday, June 20, 2019 – 1:45 PM THE SUBTLE INTERACTIONS BETWEEN POLYCYCLIC AROMATIC HYDROCARBONS AND OTHER ASTRO- Room: 116 Roger Adams Lab CHEMICALLY RELEVANT MOLECULES Chair: Amanda Steber, Universitat¨ Hamburg, Hamburg, Germany AMANDA STEBER, CRISTOBAL PEREZ, SEBASTIEN´ GRUET, DONATELLA LORU, FS-SMP, Deutsches Elektronen-Synchrotron (DESY), Hamburg, Germany; BERHANE TEMELSO, Division of Information Technol- ogy, College of Charleston, Charleston, SC, USA; GEORGE C SHIELDS, Department of Chemistry, Furman University, Greenville, SC, USA; MELANIE SCHNELL, FS-SMP, Deutsches Elektronen-Synchrotron (DESY), Hamburg, Germany. RG01 INVITED TALK 1:45 – 2:15 TOWARD UNDERSTANDING CHEMICAL EVOLUTION ALONG PROTOPLANETARY DISK FORMATION The roles that polycyclic aromatic hydrocarbons (PAHs) play in the interstellar medium (ISM) are thought to be quite diverse, from ice grain interactions to hydrogen production. Because of the importance that these roles would have in the NAMI SAKAI, Cluster for Pioneering Research, RIKEN, Saitama, Japan. ISM, we are interested in using structural information obtained via microwave spectroscopy to disentangle the first interactions between PAHs and astronomically relevant molecules. To do this, we have used chirped pulse Fourier transform microwave Star and planet formation is one of the most fundamental structure-formation processes in the Universe. Physical pro- (CP-FTMW) spectroscopy to investigate PAHs clustered with astronomical constituents, such as water. The PAHs vary cesses of star and planet formation have widely been investigated as one of the major targets of observational astronomy and in size and aromaticity, creating different preferred binding motifs of the clustered molecule(s). By using isotopic data astrophysics during the last few decades. Meanwhile, star and planet formation is inevitably accompanied with the evolution (either measured in natural abundance or through isotopically enriched samples) exact structural data has been gathered. A of interstellar matter. Increasing observational sensitivity allows us to identify about 200 interstellar molecules so far. This comparison of these systems will be presented with an in depth look at the different binding interactions present in each indicates high chemical complexity of interstellar clouds and star-forming regions despite their extreme physical condition of cluster and their binding motifs. low temperature (10-100 K) and low density (102-107 cm−3). Such chemical complexity would ultimately be related to an origin of a huge variety of substances in the Solar System. Thus, both physical and chemical approaches are indispensable to bridge star/planet formation studies and the Solar System science. In the last two decades, it is clearly demonstrated that envelopes and disks around solar-type protostars have significant COBLENTZ AWARD 11:10 chemical diversity: some sources harbor various saturated-”complex”-organic molecules (COMs) such as HCOOCH3 and Presentation of Award by Linda Kidder-Yarlott, Coblentz Society (CH3)2O, whereas some others harbor unsaturated species instead. The chemical diversity would originate from different duration time of the starless core phase of each protostar. In fact, sources showing intermediate-type of chemistry have also been found. On the other hand, the most interesting issue to be studied is how the chemical diversity in the protostellar RA04 Coblentz Society Award Lecture 11:15 – 11:55 envelopes/disks is brought into the later stages toward protoplanetary disks. Fortunately, such studies are now feasible with OPTICAL FREQUENCY COMB FOURIER TRANSFORM SPECTROSCOPY high sensitivity and angular-resolution capabilities of ALMA (Atacama Large Millimeter/Submillimeter Array). During its 7 year/cycle operation, spectacular images are being obtained after another by ALMA. These results have newly reminded us ALEKSANDRA FOLTYNOWICZ, Department of Physics, Umea University, Umea, Sweden. of a lack of sufficient information on molecular properties, such as accurate rest frequencies of molecular lines, desorption mechanism of molecules, isotopic fractionations of molecules, and so on. Modern importance of molecular science in relation Fourier transform spectroscopy (FTS) based on optical frequency combs offers a number of advantages over conventional to astronomy will be discussed by introducing recent observations with ALMA. Fourier transform infrared (FTIR) spectroscopy based on incoherent sourcesa. The high spectral brightness of the comb sources allows measuring spectra with high signal-to-noise ratios in acquisition times of the order of seconds. What is more, the resolution of comb-based FTS is given by the linewidth of the comb modes rather than the optical path difference (OPD) in the spectrometer, provided that the OPD is matched to the inverse of the comb mode spacingb. This implies that spectra with kHz resolution can be measured using OPD of the order of a few tens of cmc, which is impossible in conventional FTIR RG02 2:21 – 2:36 spectrometers. To increase the sensitivity of direct absorption measurements, frequency combs can be efficiently coupled into DUST POLARIZATION IN PROTOPLANETARY DISKS: EVIDENCE FOR MULTIPLE MECHANISMS AT WORK enhancement cavities that increase the interaction length with the sampled. In another cavity-enhanced approach, the profiles of the cavity modes are measured directly, and complex refractive index spectra of entire molecular bands are determined from RACHEL E. HARRISON, Astronomy, University of Illinois at Urbana-Champaign, Urbana, IL, USA;LESLIE e the broadening and shift of the cavity modes caused by the molecular sample . Comb-based FTS can also be combined with LOONEY, Department of Astronomy, University of Illinois at Urbana-Champaign, Urbana, IL, USA;IAN other detection methods, such as Faraday rotation spectroscopy to detect broadband interference-free spectra of paramagnetic STEPHENS, Radio and Geoastronomy Division, Harvard-Smithsonian Center for Astrophysics, Cambridge, MA, f g molecules , or photoacoustic spectroscopy that allows detection in a very small sample volume . I will present the various USA; ZHI-YUN LI, Department of Astronomy, The University of Virginia, Charlottesville, VA, USA;HAIFENG implementations of comb-based FTS and show examples of high-resolution measurements of entire absorption bands in the YANG, Institute for Advanced Study, Tsinghua University, Beijing, China; AKIMASA KATAOKA, , National near- and mid-infrared wavelength range. Astronomical Observatory of Japan, Tokyo, Japan; ROBERT J HARRIS, Department of Astronomy, University

aJ. Mandon, G. Guelachvili, and N. Picque, Nat. Photonics 3, 99 (2009). of Illinois at Urbana-Champaign, Urbana, IL, USA; WOOJIN KWON, Radio Astronomy, Korea Astronomy and bP. Maslowski, et al., Phys. Rev. A 93, 021802 (2016); L. Rutkowski, et al., J. Quant. Spectrosc. Radiat. Transf. 204, 63 (2018). Space Science Institute, Daejeon, Republic of Korea; TAKAYUKI MUTO, Division of Liberal Arts, Kogakuin cL. Rutkowski, et al., Opt. Express 25, 21711 (2017). University, Tokyo, Japan; MUNETAKE MOMOSE, Center for Astronomy, Ibaraki University, Mito, Japan. dM. J. Thorpe, and J. Ye, Appl. Phys. B 91, 397 (2008); A. Foltynowicz, et al., Phys. Rev. Lett. 107, 233002 (2011). eA. C. Johansson, et al., Opt. Express 26, 20633 (2018). fA. C. Johansson, J. Westberg, G. Wysocki, and A. Foltynowicz, Appl. Phys. B 124, 79 (2018). The surfaces of astronomical dust grains are a crucial site for chemical reactions. Observations of polarized emission gI. Sadiek, et al., Phys. Chem. Chem. Phys. 20, 27849 (2018). from dust grains provide a powerful tool for investigating the sizes and distribution of dust grains in protoplanetary disks. We present ALMA observations of three protostellar disks at 3 mm and 870 μm: Haro 6-13, RY Tau, and MWC 480. At 870 μm, all three disks show polarization morphologies consistent with those produced by self-scattering. At 3 mm, Haro 6-13 shows a polarization morphology that may indicate radiative or mechanical alignment of grains, while RY Tau and MWC 480 still show polarization patterns that are consistent with scattering. Additionally, we present models of the polarization patterns different polarization mechanisms would be expected to produce in these disks. 188 189

RG03 2:39 – 2:54 RG05 3:51 – 4:06 THE DEVELOPMENT OF A SUBMILLIMETER SPECTROSCOPIC METHOD FOR DETECTING PHOTODESORBED CONSTRAINING THE FORMATION OF FUNDAMENTAL INTERSTELLAR MOLECULES USING ISOTOPO- ICES LOGUES

KATARINA YOCUM, AYANNA JONES, ETHAN TODD, SUSANNA L. WIDICUS WEAVER, Department of OLIVIA H. WILKINS, Chemistry, California Institute of Technology, Pasadena, CA, USA; BRANDON CAR- Chemistry, Emory University, Atlanta, GA, USA; STEFANIE N MILAM, Astrochemistry, NASA Goddard Space ROLL, Atomic and Molecular Physics, Harvard-Smithsonian Center for Astrophysics, Cambridge, MA, USA; Flight Center, Greenbelt, MD, USA. GEOFFREY BLAKE, Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, CA, USA. This work aims to reveal new information about the gas and ice compositions of early star-forming regions and plane- tary/cometary atmospheres. To shed light on this topic, a new approach for analyzing the desorbed products of laboratory The formation of so-called complex molecules in the early stages of star formation has implications not only for how we ices is being developed. The technique consists of the submillimeter spectroscopic analysis of thermally and photo-processed decipher the evolution of planetary systems but also how we understand the evolution of molecules themselves. Interstellar ices. This is the same spectroscopic technique used to remotely probe gas-phase compositions of interstellar space and plane- complex molecules, which are simple by terrestrial standards, with only six or more atoms, are key precursors to the rich tary/cometary atmospheres. Therefore, the laboratory spectroscopic data provided are directly comparable to spectra collected chemical diversity found in comets and meteorites and on planetary bodies. Isotopologues have proven useful in other areas of via ground- and space-based telescopes. Furthermore, this technique is capable of distinguishing branching ratios of desorbed chemistry, for instance in pinning down formation mechanisms of molecules in synthetic organic chemistry, but there has been isomers, something that traditional laboratory ice studies have always struggled with. Experimental design and new results relatively little work done using isotopologues to understand how interstellar molecules form. Isotopologues have been used, will be discussed. however, in constraining the formation of molecules such as methyl cyanide (CH3CN) and methanol (CH3OH)intheOrion Kleinmann-Low nebula (Orion KL). Previous low-spatial-resolution studies of methanol in Orion KL have been inconclusive, and thus we have obtained high-resolution imaging data of deuterated methanol (CH2DOH, CH3OD) toward Orion KL with the Atacama Large Millimeter/submillimeter Array (ALMA). These data show the distribution of deuterated methanol on 13 spatial scales commensurate with local star formation. Comparing the ratios of CH2DOH and CH3OD with CH3OH,we aim to assess how methanol chemistry varies across the nebula and determine observationally whether the molecule is formed predominantly on the surfaces of icy dust grains as predicted by laboratory experiments and computational models. These results will be discussed as will the use of isotopologues in the laboratory. Constraining the formation of complex organic molecules in star-forming regions is a first step in understanding how even more complex chemistry—perhaps even prebiotic chemistry—evolved over the history of the universe.

RG04 2:57 – 3:12 LASER ABLATION OF SOLID ORGANIC PRECURSORS AS AN ALTERNATIVE TOOL IN THE GENERATION OF INTERSTELLAR MOLECULES

LUCIE KOLESNIKOVA´ a,IKERLEON,´ ELENA R. ALONSO, SANTIAGO MATA, JOSE´ L. ALONSO, Grupo de Espectroscopia Molecular, Lab. de Espectroscopia y Bioespectroscopia, Unidad Asociada CSIC, Universidad RG06 4:09 – 4:24 de Valladolid, Valladolid, Spain. FIRST DETECTION OF THE RADIOACTIVE MOLECULE 26AlF AND ITS SPECTROSCOPIC ASPECTS In the course of the investigation of the rotational spectrum of prebiotic hydantoic acid by Fourier transform microwave spectroscopy coupled to a laser ablation source in a supersonic expansion, rotational signatures of two cyclic molecules, hy- ALEXANDER A. BREIER, GUIDO W FUCHS, THOMAS GIESEN, Institute of Physics, University Kassel, dantoin and 2,5-oxazolidinedione, have been unexpectedly observed along with the four most stable conformers of hydantoic Kassel, Germany;JURGEN¨ GAUSS, Institut fur¨ Physikalische Chemie, Universitat¨ Mainz, Mainz, Germany; acid.b Interestingly, two of them presented folded geometric arrangements that might act as precursors in the cyclization reac- TOMASZ KAMINSKI, , Harvard-Smithsonian Center for Astrophysics, Cambridge, MA, USA. tions assisted by laser ablation. They could play the role of near-attack conformations (NACs) in the framework of the NAC 26 theory for intramolecular reactions. A detailed analysis of the spectrum further revealed the simultaneous formation of other The observation of radioactive isotopes, like Al, gives insights in the earlier nucleosynthesis processes of stellar cores. species in the jet, showing that the laser ablation of solid organic precursors constitutes an alternative tool in the generation Until now, the characteristic γ-photons released during radioactive decay have been used to record their spatial distribution b on a large scale, but this method generally fails to identify individual stellar objects due to the limited detection sensitivity. of new chemical species. It has been recently confirmed using diaminomaleonitrile as a solid precursor. Up to 30 different 26 27 species (most of them detected in space) have been revealed in the supersonic expansion of our laser ablation chirped pulse An alternative approach is the observation of molecules containing radioactive isotopes, like AlF. The stable Al-bearing Fourier transform microwave LA-CP-FTMW experiment. molecule is known to condensate in the outer atmosphere of late-type stars. Radio-telescope facilities, like ALMA,can identify these species via their rotational fingerprint. To enable an unambiguous identification the rotational transition 26 aDepartment of Analytical Chemistry, University of Chemistry and Technology, Prague, Czech Republic. frequencies of AlF need to be known with high accuracy. bKolesnikova,´ L.; Leon,´ I.; Alonso, E. R. et al.: J. Phys. Chem. Lett. 2019, accepted, DOI: 10.1021/acs.jpclett.9b00208. In this work, the first detection of 26AlF in the merger object CK Vulpeculae is reported. The mass-independent molecular parameterization of AlF using a Dunham approach is shown in detail. Further candidate stellar sources of 26Al will be discussed.

Intermission 190 191

RG07 4:27 – 4:42 RG09 5:03 – 5:18

INVESTIGATING ISOMERS OF ASTROPHYSICAL MOLECULES BY ROTATIONAL SPECTROSCOPY: THE CASE GLOBAL ANALYSIS OF THE NH2 RADICAL ROTATIONAL, VIBRATIONAL AND ELECTRONIC TRANSITIONS OF [C2H2O] COMPOUNDS MARIE-ALINE MARTIN-DRUMEL, OLIVIER PIRALI, L. H. COUDERT, Institut des Sciences Moleculaires´ MARIE-ALINE MARTIN-DRUMEL, CNRS, Institut des Sciences Moleculaires d’Orsay, Orsay, France; d’Orsay, Universite´ Paris-Sud, Orsay, France. KELVIN LEE, Radio and Geoastronomy Division, Harvard-Smithsonian Center for Astrophysics, Cambridge, a b MA, USA; OLIVIER PIRALI, AILES beamline, Synchrotron SOLEIL, Saint Aubin, France; J.-C. GUILLEMIN, The NH2 radical, first observed by Herzberg and Ramsay, is dominated by a strong Renner-Teller effect giving rise to ˜ 2 ˜ 2 UMR 6226 CNRS - ENSCR, Institut des Sciences Chimiques de Rennes, Rennes, France;MICHAELCMc- two electronic states: a bent X B1 ground state and a quasi-linear A A1 excited state. The NH2 radical has been the subject CARTHY, Atomic and Molecular Physics, Harvard-Smithsonian Center for Astrophysics, Cambridge, MA, USA. of numerous high-resolution investigations and its rotational, vibrational, and electronic transitionsc have been measured. In the most recent investigation,c a value of the rotational quantum number N as large as 26 could be reached and the line position ˜ 2 Detection of isomers in the interstellar medium is a valuable tool toward a better understanding of the formation and analysis revealed that, even in the X B1 ground electronic state, an anomalous centrifugal distortion occurs and originates d destruction mechanisms at play, especially because kinetics effects are thought to be as important as thermodynamic ones, if from the strong coupling between the overall rotation and the bending ν2 mode, as in the case of the water molecule. not preponderant. About a third of the interstellar species discovered so far are isomers but little remains known on reactive Two theoretical approaches accounting for the Renner-Teller effect are setup to compute the rovibronic energy levels of isomers of relatively large astrophysical species (5 atoms and more), in part due to the difficulty to both produce and detect NH2. The first one is an effective approach in which the large amplitude bending mode and the overall rotation are treated these species in the laboratory. simultaneously.e The second one is an exact approach, based on a tridimensional potential energy surface, in which all three Ketene is one such species: the molecule is a known interstellar species but none of its isomers has so far been detected vibrational modes are considered in addition to the overall rotation.f by mean of rotational spectroscopy, preventing any interstellar detection so far. We have undertaken an experimental and In the talk, both approaches will be tested fitting experimental high-resolution data pertaining to the NH2 radical. The theoreticcal investigation of the rotational spectrum of the isomers of ketene, and in particular of its two close-shell isomers, first approach will be applied to data involving the ground and (010) vibrational states. The second approach should allow us hydroxyacetylene (HCCOH) and oxirene (c-C2H2O). We will report our results on these compounds and propects of using to treat any vibrational states and to adjust the tridimensional potential energy surface of the radical.g a recent experimental technique – spectral taxonomy – to investigate isomers of astrophysical interest in the millimeter and aHerzberg and Ramsay, J. Chem. Phys. 20 (1952) 347 submillimeter domains. bDressler and Ramsay, Phil. Trans. R. Soc. A 25 (1959) 553 cHadj Bachir, Huet, Destombes, and Vervloet, J. Molec. Spectrosc. 193 (1999) 326; McKellar, Vervloet, Burkholder, and Howard, ibid. 142 (1990) 319; Morino and Kawaguchi, ibid. 182 (1997) 428; and Martin-Drumel, Pirali, and Vervloet, J. Phys. Chem. A 118 (2014) 1331 dCamy-Peyret and Flaud, Molec. Phys. 32 (1976) 523 eCoudert, Gans, Garcia, and Loison, J. Chem. Phys. 148 (2018) 054302 fCoudert, Gans, Holzmeier, Loison, Garcia, Alcaraz, Lopes, and Roder,¨ J. Chem. Phys. 149 (2018) 224304 gJensen, Odaka, Kraemer, Hirano and Bunker, Spectrochim. Acta Part A 58 (2002) 763

RG08 4:45 – 5:00 SUBMILLIMETER WAVE SPECTROSCOPY AND ISM SEARCH FOR PROPIONIC ACID

L. MARGULES` ,R.A.MOTIYENKO,UMR 8523 - PhLAM - Physique des Lasers Atomes et Molecules,´ Uni- versity of Lille, CNRS, F-59000 Lille, France; V. ILYUSHIN, OLGA DOROVSKAYA, E. A. ALEKSEEV, Ra- diospectrometry Department, Institute of Radio Astronomy of NASU, Kharkov, Ukraine; ELENA R. ALONSO, LUCIE KOLESNIKOVA,´ Grupo de Espectroscopia Molecular, Lab. de Espectroscopia y Bioespectroscopia, Unidad Asociada CSIC, Universidad de Valladolid, Valladolid, Spain; JOSE CERNICHARO, Instituto de Fisica Fundamental, CSIC, Madrid, Spain; J.-C. GUILLEMIN, UMR 6226 CNRS - ENSCR, Institut des Sciences Chim- iques de Rennes, Rennes, France.

Two compounds with a C2H4O2 formula have been detected in the Interstellar Medium (ISM): acetic acid (CH3CO2H) and methyl formate (CH3OC(O)H), the latter being thermodynamically less stable than the former but more abundant. Among the higher homologues with a C3H6O2 formula where a hydrogen atom in C2H4O2 has been replaced by a CH3 group, two compounds have already been detected: ethyl formate (EtOC(O)H) and methyl acetate (CH3OC(O)CH3). The higher thermodynamic stability of another isomer, the propionic acid (EtCO2H), pushed us to record its rotational spectrum, since this compound has a high probability of being present in the ISM. The methyl top internal rotation should be taken into account, therefore the analysis is performed using RAM36 code.a The spectroscopic results and its search in ISM will be presented. This work was supported by the CNES and the Action sur Projets de l’INSU, PCMI

aIlyushin, V.V. et al;J. Mol. Spectrosc. 259, (2010) 26 192 193 RH. Mini-symposium: Non-covalent Interactions Thursday, June 20, 2019 – 1:45 PM RH04 2:39 – 2:54 Room: 100 Noyes Laboratory HYDROGEN BONDING IN THE MONOHYDRATES AND HOMODIMERS OF CYCLOHEXYLAMINE AND CYCLO- Chair: Rebecca A. Peebles, Eastern Illinois University, Charleston, IL, USA HEXANETHIOL

MARCOS JUANES, RIZALINA TAMA SARAGI, ALBERTO LESARRI, Departamento de Qu´ımica F´ısica RH01 1:45 – 2:00 yQu´ımica Inorganica,´ Universidad de Valladolid, Valladolid, Spain; RUTH PINACHO, JOSEEMILIANO´ THE STYRENE OXIDE DIMER STORY RUBIO, Departamento de Electronica,´ ETSIT, University of Valladolid, Valladolid, SPAIN; LUCA EVANGE- LISTI, Dipartimento di Chimica G. Ciamician, Universita` di Bologna, Bologna, Italy;DANIELA.OBEN- SERGIO R DOMINGOS, MELANIE SCHNELL, FS-SMP, Deutsches Elektronen-Synchrotron (DESY), Ham- CHAIN, JENS-UWE GRABOW, Institut fur¨ Physikalische Chemie und Elektrochemie, Gottfried-Wilhelm- burg, Germany. Leibniz-Universitat,¨ Hannover, Germany.

a The processes that govern aggregation at the molecular level are loosely established. Molecular recognition is mediated Following previous investigation of the monohydrate and homodimer of cy- b via a delicate balance between the prevailing intermolecular interactions at play, hydrogen bonding and dispersion interac- clohexanol , we have examined the non-covalent interactions in the saturated tions. Using high-resolution broadband rotational spectroscopy and supersonic jets, we studied the styrene oxide dimer. Due six-membered rings of cyclohexylamine (CA) and cyclohexanethiol (CT), using to its chirality, these dimers exist as enantiomeric and diastereomeric pairs, with the diastereomers being directly differen- chirped-pulsed and cavity Fourier-transform microwave spectroscopy (2-18 GHz). tiable via their rotational spectra. Interestingly, the three most stable styrene oxide dimers are stabilized by three intermolec- Water behaves as proton donor to both CA and CT, generating two isomers in CT ··· ··· ular contacts, arising from two CH-O and π-π interactions. The phenyl groups show a similar arrangement as in the case of H2O (equatorial-gauche and equatorial-trans) and a single isomer in CA H2O ··· the parallel-displaced benzene dimer. The next set of dimers, which are slightly higher in energy, is stabilized by two CH-π (equatorial gauche-trans). Torsional splittings were observed for CT H2O, while interactions each. The interplay between hydrogen bonding and dispersion on the formation of these homo- and heterodimers nuclear quadrupole coupling effects were resolved for CA ··· H2O. The predicted as well as their prospects for chiral tagging will be discussed. hydrogen bond distances in the hydrated amine and thiol are enlarged with respect to the alcohol (rOH···S)=2.47Aand(r˚ O−H ···N )=1.91Avs(r˚ O−H ···O)=1.88A).˚ Work on the CA2 and CT2 dimers will also be reported. In these dimers the hy- RH02 2:03 – 2:18 drogen bonds are characterized by rO−H ···O=1.88Aandr˚ O−H ···N =1.91 A.˚ Rota- THE CONVERSION OF STYRENE OXIDE ENANTIOMERS INTO SPECTROSCOPICALLY DISTINGUISHABLE DI- tional data and supporting ab initio calculations will be presented for the investi- ASTEREOMERS THROUGH COMPLEXATION WITH 3,3,3-TRIFLUORO-1,2-EPOXYPROPANE gated species.

aM. Juanes, W. Li, L. Spada, L. Evangelisti, A. Lesarri, W. Caminati, Phys.Chem.Chem.Phys., 2019, 21, 3676. MARK D. MARSHALL, HELEN O. LEUNG, Chemistry Department, Amherst College, Amherst, MA, USA; bM. Juanes, I. Leon,´ R. Pinacho, J. E. Rubio, W. Li, L. Evangelisti, W. Caminati, A. Lesarri, Comm. WK09, 73rd ISMS (Urbana-Champaign), 2018. MELANIE SCHNELL, SERGIO R DOMINGOS, ANNA KRIN, FS-SMP, Deutsches Elektronen-Synchrotron (DESY),Hamburg,Germany.

3,3,3-Trifluoro-1,2-epoxypropane [2-(trifluoromethyl)-oxirane, or TFO] has shown promise as a tag for chiral analysis through conversion of enantiomers into spectroscopically distinguishable diastereomers via the formation of non-covalently bound heterodimers. We demonstrate the suitability of this method through characterization of the microwave rotational spectrum of complexes formed between TFO and styrene oxide (SO). Molecular dynamics calculations are used to quickly RH05 2:57 – 3:12 identify possible heterodimer conformations which are then optimized and evaluated using density functional theory. Using DISPERSION AND HYDROGEN BOND INTERACTIONS IN LARGE COMPLEXES: THE DIADAMANTHYL ETHER a mixture of racemic samples of both species, we observe and assign spectra for the lowest energy conformers of both CASE homochiral (RR/SS)-TFO-SO and heterochiral (RS/SR)-TFO-SO. Had a single enantiomer of TFO been used, say (R), the spectra are sufficiently distinct and sufficiently well predicted by theory that (RR)-TFO-SO and (RS)-TFO-SO are readily MARIA´ MAR QUESADA-MORENO, PABLO PINACHO, CRISTOBAL PEREZ, FS-SMP, Deutsches identified and separately analyzed. Elektronen-Synchrotron (DESY), Hamburg, Germany; MARINA SEKUTOR, PETER R. SCHREINER, Insti- tute for Organic Chemistry, Justus Liebig University of Giessen, Giessen, Germany; MELANIE SCHNELL, RH03 2:21 – 2:36 FS-SMP, Deutsches Elektronen-Synchrotron (DESY), Hamburg, Germany.

THE MICROWAVE SPECTRUM AND MOLECULAR STRUCTURE OF THE CHIRAL TAGGING CANDIDATE, 3- The large diadamanthyl ether (DME, C20H30O) molecule presents a good model to study the interplay between dis- FLUORO-1,2-EPOXYPROPANE (EPIFLUOROHYDRIN), AND ITS COMPLEX WITH THE ARGON ATOM persion and hydrogen bond interactions. In this work, we have studied different diadamanthyl ether complexes where the sizes and the steric complexity of the partners were systematically changed. In addition, their contributions to dispersion and MARK D. MARSHALL, HELEN O. LEUNG, DEVON J. STUART, Chemistry Department, Amherst College, hydrogen bond interactions were different to create a broad overview. On the one side, we have analyzed the structures and Amherst, MA, USA. different interactions taking place between DME and a series of alcohol aggregates, that is, water (finding clusters up to 3 molecules of water), ethanol and tert-butanol. On the other side, we have studied the complexes formed between DME and Continuing our efforts in characterizing small molecules for use as potential chiral tags for the conversion of enantiomeric benzene, hexafluorobenzene and phenol. All these structures have been studied in the gas phase under the cold and isolated molecules into spectroscopically distinct diastereomeric complexes for chiral analysis, we examine the microwave spectrum conditions of a supersonic expansion. To analyze them, we have used the highly sensitive and high resolution chirped pulse and molecular structure of 3-fluoro-1,2-epoxypropane. Although this species has a lower vapor pressure than the trifluoro- Fourier transform microwave (CP-FTMW) spectroscopy in the 2-8 GHz region. Quantum chemical calculations were per- and difluoro- analogues previously reported at this meeting, it is still relatively easy to incorporate into a free jet expansion formed to aid the analysis of the experimental data. The results obtained can help to understand the influence of the interplay by flowing a carrier gas over a heated liquid sample. In common with the structurally similar trifluoro- and difluoro- species, between dispersion and hydrogen bond interactions on the formation and stabilization of the structures of large complexes. it has a simple, hyperfine-free rotational spectrum. This spectrum has been obtained for the most abundant and four singly- substituted isotopologues, all in natural abundance, and the structure of the molecule determined. Multiple minima of similar energies are predicted for the complex of 3-fluoro-1,2-epoxypropane with argon, and progress on assigning and analyzing the spectra of these complexes will be reported. Intermission 194 195

RH06 3:51 – 4:06 RH08 4:27 – 4:42 STRUCTURES OF COMPLEXES OF CYCLOOCTANONE WITH WATER DIMERIZATION AND MICROSOLVATION OF 2- AND 3-THIOPHENEETHANOL

ECATERINA BUREVSCHI,ISABELPENA,˜ M. EUGENIA SANZ, Department of Chemistry, King’s College MARCOS JUANES, RIZALINA TAMA SARAGI, ALBERTO LESARRI, Departamento de Qu´ımica F´ısica y London, London, United Kingdom. Qu´ımica Inorganica,´ Universidad de Valladolid, Valladolid, Spain; LOURDES ENRIQUEZ, MARTIN JARAIZ, Departamento de Electronica,´ ETSIT, University of Valladolid, Valladolid, SPAIN. Water is present in the air with a concentration of up to 4 %, and also in the olfactory mucosa. Odorants are thus very We are using rotational spectroscopy to exam- likely to interact with water before reaching olfactory recep- ine sulfur hydrogen bonding in a series of thiophene tors. We have investigated the complexes of cyclooctanone with and furan mercapto derivativesa, in order to compare water as a first step towards understanding how larger macro- their aggregation properties with those of the equiv- cyclic odorants interact with water. Two complexes of the most alent alcohols. Here we report on the dimers and abundant conformer of cyclooctanone with one water molecule, monohydrates of 2-thiopheneethanol (2TE) and 3- and two complexes with two water molecules have been charac- thiopheneethanol (3TE), isolated in a jet-cooled ex- terised using chirped-pulse Fourier Transform Microwave (CP- pansion. Two isomers of (2TE)2, three isomers of FTMW) spectroscopy. In the cyclooctanone-H2O complexes, (3TE)2 and the two monohydrates 2TE···H2Oand water forms a O–H...O hydrogen bond with the carbonyl oxy- 3TE···H2O were observed using chirped-pulsed and gen of cyclooctanone and two O...H–C hydrogen bonds with the cavity Fourier transform microwave spectroscopy –CH2 groups in the cyclooctanone ring. In the cyclooctanone- (2-18 GHz). The dimers are primary bound in all (H2O)2 complexes, the second molecule of water binds pri- cases by the stronger O-H···O interaction (rO−H ···O marily to the first molecule of water through hydrogen bond- ca. 1.88 A)˚ originated by the alcohol groups. In the ing, whilst also forming secondary interactions with the –CH2 monohydrates water behaves as a proton acceptor, groups in the ring. The observation of all 13C isotopic species and the spectrum shows evidence of torsional tun- of the cyclooctanone ring in the complexes in their natural abun- neling. Rotational parameters and supporting ab initio calculations will be reported. dances, and of the 18O species using isotopically enriched water allowed us to calculate the experimental structures of the aM. Juanes, A. Lesarri, R. Pinacho, E. Charro, J. E. Rubio, L. Enr´ıquez, M. Jara´ız, Chem. Eur. J., 2018, 24, 6564 complexes.

RH07 4:09 – 4:24

THE COMPETITION AND COOPERATIVITY OF NON-COVALENT BONDS IN BENZOPHENONE-(H2O)1,2,3 CLUS- TERS REVEALED BY BROADBAND MICROWAVE SPECTROSCOPY

WEIXING LI, PABLO PINACHO, MARIA´ MAR QUESADA-MORENO, MELANIE SCHNELL, FS-SMP, Deutsches Elektronen-Synchrotron (DESY), Hamburg, Germany.

Herein, the pure rotational spectra of benzophenone complexed with up to three water molecules were observed by us- ing chirped-pulse Fourier transform microwave (CP-FTMW) spectroscopy. Benzophenone offers dispersion interaction sites through the phenyl rings and a hydrogen bond acceptor through the carbonyl oxygen, allowing us to study the competing bind- ing sites for water molecules. The theoretical calculation combined with the isotopic substitution measurement provides the unambiguous structural information of the complexes. In benzophenone-(H2O)1,2 clusters, the water molecules are located at one side of a phenyl group, where benzophenone and water molecules form a ring. Water monomer or dimer links with the carbonylgroupthroughanOH...Ohydrogenbond and links with the phenyl group through a CH. . . O weak hydrogen bond. The benzophenone-(H2O)3 complex is of interest as the water trimer was found located at the top of one phenyl group with the cooperativity of the hydrogen bond net. The water trimer forming an open loop through two hydrogen bonds is locked by benzophenone through one OH...O,oneOH...π, and one CH. . . O hydrogen bonds, respectively. 196 197 RI. Rotational structure/frequencies RI03 2:21 – 2:36 Thursday, June 20, 2019 – 1:45 PM ROTATIONAL SPECTROSCOPY OF SILICON-NITROGEN MOLECULES: SiH3NC AND NH2Si

Room: 1024 Chemistry Annex KELVIN LEE, Radio and Geoastronomy Division, Harvard-Smithsonian Center for Astrophysics, Cambridge, MA, USA; G. STEPHEN KOCHERIL, Department of Chemistry, Brown University, Providence, RI, USA;CARL Chair: Kenneth R. Leopold, University of Minnesota, Minneapolis, MN, USA A GOTTLIEB, Radio and Geoastronomy Division, Harvard-Smithsonian Center for Astrophysics, Cambridge, MA, USA; MICHAEL C McCARTHY, Atomic and Molecular Physics, Harvard-Smithsonian Center for Astro- physics, Cambridge, MA, USA.

Silicon-nitrogen compounds are an important class of molecules, with implications in fields ranging from molecular astrophysics as refractory species in evolved stars, and in terrestrial applications such as chemical vapor deposition. In this talk, we present the gas-phase detection and microwave rotational spectroscopy of two new silicon-nitrogen molecules: ˜ 1 ˜ 2 silyl isocyanide (SiH3NC, X A1) and aminosilane (H2NSi, X B2). Both species are readily produced in an electrical discharge, combining silane (SiH4) with either methyl cyanide (CH3CN) or ammonia (NH3) to produce the species of RI01 1:45 – 2:00 interest. Using Fourier-transform and double resonance microwave spectroscopy, we were able to measure the three lowest rotational transitions (at 10, 20, 30 GHz) for SiH3NC,andforH2NSi, the two lowest transitions at 30 and 60 GHz. By BENZENE’S INFERNO. PART I: A MICROWAVE SPECTROSCOPIC INVESTIGATION 15 substituting the precursors for rare-isotope enriched ones (e.g. NH3), we were able to extend the measurements to several 15 13 15 MICHAEL C McCARTHY, Atomic and Molecular Physics, Harvard-Smithsonian Center for Astrophysics, isotopologues: SiH3 NC and SiH3N C for silyl isocyanide, and H2 NSi, D2NSi for aminosilane. The experiments are Cambridge, MA, USA; KELVIN LEE, Radio and Geoastronomy Division, Harvard-Smithsonian Center for As- supplemented by high level quantum chemical calculations, which provided predictions of rotational constants, multipole trophysics, Cambridge, MA, USA. moments, and in the case of aminosilane, the spin-rotation interaction tensor elements.

Benzene is of central importance in combustion chemistry because formation of the first aromatic ring is the rate-limiting step in polycyclic aromatic hydrocarbon (PAH) growth. For these reasons, the fragmentation and isomerization of benzene are highly topical, as are intermediates formed in route to larger rings. Using a combination of broadband and cavity Fourier- transform microwave spectroscopies and newly developed analysis and assignment tools, the discharge products of benzene have been extensively studied in the 2-19 GHz frequency range. In addition to rotational transitions from 30 known species, evidence has been found for eight entirely new hydrocarbon molecules; these species include both branched and chain frag- ments of benzene, high energy isomers, and larger molecules such as phenyldiacetylene and isomers of fulvenallene; together they account for nearly 1/3 of the observed transitions, and about 1/2 of the spectral intensity. Benzene fragmentation and isomerization, as well pathways that may lead to larger aromatic rings will be discussed in the context of the newly discovered molecules. RI04 2:39 – 2:54 A HIGH SPEED FITTING PROGRAM FOR ROTATIONAL SPECTROSCOPY

BRANDON CARROLL, Atomic and Molecular Physics, Harvard-Smithsonian Center for Astrophysics, Cam- bridge, MA, USA; KELVIN LEE, Radio and Geoastronomy Division, Harvard-Smithsonian Center for As- trophysics, Cambridge, MA, USA; MICHAEL C McCARTHY, Atomic and Molecular Physics, Harvard- Smithsonian Center for Astrophysics, Cambridge, MA, USA. RI02 2:03 – 2:18 The recent advent of chirped-pulse Fourier transform microwave (CP-FTMW) spectroscopy has dramatically increased BENZENE’S INFERNO, PART II: AUTOMATED ANALYSIS AND IDENTIFICATION the amount of data available to microwave spectroscopists. However, this information is only useful when it can be translated KELVIN LEE, Radio and Geoastronomy Division, Harvard-Smithsonian Center for Astrophysics, Cambridge, into molecular information, and ultimately chemical knowledge. With such large volumes of information, new, more sophis- MA, USA; MICHAEL C McCARTHY, Atomic and Molecular Physics, Harvard-Smithsonian Center for Astro- ticated tools are required to fully interpret the data without large increases in research hours required. Several methods, both physics, Cambridge, MA, USA. computational and experimental, have been developed to simplify and automate the assignment of microwave spectra. Such tools can also make microwave spectroscopy far more approachable and usable for non-experts. To manage the expanding With the advent of broadband microwave spectroscopy, rotational spectra can now be routinely acquired of many giga- data volumes and use cases of microwave spectroscopy, increasingly computationally efficient spectral assignment methods hertz of frequency bandwidth. When applied to chemical mixtures of unknown composition, however, spectral analysis often are desirable to enable rapid and complete spectral assignment. becomes tedious and time consuming. Electrical discharges are examples of complex mixtures with rich rotational spectra, We have recently developed a numerically efficient, high-speed program for the prediction and fitting of rotational spectra. owing to fragmentation of stable molecules and rapid chemical reactions that subsequently take place in the energetic plasma. This program is built on a simple framework that is applicable to a wide variety of molecules. We will present this program, In this talk, we describe a workflow — which we have developed in Python — for analyzing the products in a benzene dis- discuss its performance, and demonstrate its use in fitting CP-FTMW spectra. charge. The workflow is designed to be reproducible, automated, and open-source, and can be applied to help assign both laboratory and astronomical spectral line surveys. As part of this workflow, we will discuss how entirely new molecules — those that give rise to strong rotational lines but whose stoichometry and structure are unknown — can be analyzed and identified with minimal chemical intuition.

Intermission 198 199

RI05 3:33 – 3:48 RI08 4:27 – 4:42 AN EXPERIMENTALIST’S GUIDE TO ROTATIONAL CONSTANTS WITH LOW-COST THEORY MILLIMETER-WAVE SPECTRUM OF 2-CYANOPYRIDINE IN ITS GROUND STATE AND THE DYAD OF ITS LOW- EST ENERGY VIBRATIONALLY EXCITED STATES, ν30 AND ν21 KELVIN LEE, Radio and Geoastronomy Division, Harvard-Smithsonian Center for Astrophysics, Cambridge, MA, USA. P. MATISHA DORMAN, BRIAN J. ESSELMAN, R. CLAUDE WOODS, ROBERT J. McMAHON, Depart- ment of Chemistry, The Univeristy of Wisconsin, Madison, WI, USA. Microwave spectroscopy is a widely applied tool for determining molecular structures, studying molecular astrophysics, and in more recent times decomposing complex mixtures. All of these applications are made possible due to the tight connec- In this study, we collected the 135-375 GHz rotational spectrum of 2-cyanopyridine, a N-heteroatom analog of the tion between the observable rotational transitions and a molecule’s rotational constants, which in turn depend on its principal interstellar molecule, benzonitrile. 2-Cyanopyridine’s strong dipole moment (μa =5.5 D, μb =1.9 D) and the fact that it is a moments of inertia. Electronic structure calculations are often used to provide predictions of rotational constants, although cyano substituted aromatic molecule make it another attractive species for detection by radioastronomy. The ground state of much like other molecular properties, the accuracy depends heavily on the method and basis used. Accurate estimates based 2-cyanopyridine was fit to a centrifugally distorted single state model using Kisiel’s ASFIT (Nlines ∼ 6500, σ =0.043)and b a b on ”proper” quantum chemistry require highly correlated methods such as coupled-cluster theory, along with large basis sets primarily includes R−1,1, R0,1, and R1,1 type lines. The two lowest fundamentals, ν30 and ν21, display effects of strong that incorporate effects such as core-valence electron correlation and scalar relativity. For larger molecules, this approach Coriolis interactions and require treatment via a two-state model. Discreet local resonances with ΔKa =3perturbation have remains intractable due to the excessive computational cost, thus empirical scaling of low-cost theoretical constants is highly been seen along with the effects of a strong a-type global perturbation. Currently, using Pickett’s SPFIT, around 16,000 distinct desirable. In this talk, we will present a large systematic benchmark study comprising 11 commonly used low-cost electronic rotational transitions for these states have been measured, from Ka =0to 49 and J” = 11 to 146, leading to an experimental −1 −1 structure theories, 7 basis sets, and 78 closed-shell species of varying elemental composition. By comparing with experi- energy difference of ΔE30,21 = 793379.9 MHz (∼ 26.5 cm , compared to a 30.6 cm B3LYP/6-311+G(2d,p) anharmonic J J K mentally determined values, our analysis ranks the performance of each method/basis combinations in our set, highlighting frequency prediction). Six perturbation terms, including Ga,Gb,Fbc and the higher order terms, Ga ,Gb ,Gb , are currently the best combinations and revealing potential shortcomings and weaknesses of select methods. Finally, we determine empir- being treated; and those predicted agree to within 10% of the prediction. This presentation will expand on the progress of the ical scaling constants for each method/basis combination that can be used to account for the effect zero-point vibration on two state least squares fit and full results of the millimeter-wave analysis of 2-cyanopyridine. equilibrium rotational constants. RI09 4:45 – 5:00 RI06 3:51 – 4:06 CHARACTERIZATION OF THE TRIFLUOROACETIC ANHYDRIDE MONOMER BY MICROWAVE SPEC- AN UPDATE ON THE THEORY OF ROTATIONAL ENERGY SURFACES TROSCOPY

BRADLEY KLEE, Department of Physics, University of Arkansas, Fayetteville, AR, USA. NATHAN LOVE, CJ SMITH, ANNA HUFF, KENNETH R. LEOPOLD, Chemistry Department, University of Minnesota, Minneapolis, MN, USA. In Springer’s Handbook for Atomic, Molecular, and Optical Physics, William Harter gives a semiclassical theory of Hamiltonian Rotational Energy Surfaces. Therein accurate spectral The rotational spectrum of trifluoroacetic anhydride (TFAA, CF3COOCOCF3) has been observed by chirped-pulse and estimates follow from classical precession integrals, real and complex. An analogy between the cavity Fourier transform microwave spectroscopy. Collection and processing of chirped-pulse spectra were expedited through phase plane and the phase sphere suggests that integrals along a rotational energy surface can be the use of a recently developed automation program, which will be briefly described. Over 250 transitions were recorded known to the same precision as familiar standards such as the complete elliptic integral of the between 6 and 18 GHz ranging from J” = 2 to 24. Spectra were readily fit to a Watson A-reduced Hamiltonian with no first kind. Newly developing integral-differential algorithms allow us to refine calculations on evidence of internal rotation of the CF3 groups. The experimental rotational constants and the observation of exclusively both domains. We will showcase a few results with high symmetry, and explain how they fit into b-type spectra are consistent with a staggered TFAA configuration predicted to be the global minimum by calculations at the a fully Riemannian perspective, which also improves upon the picture of tunneling phenomena. M06-2X/6-311++G(3df,3pd) level of theory.

RI10 Post-Deadline Abstract 5:03 – 5:18 RI07 4:09 – 4:24 PRECISION MEASUREMENT OF ULTRACOLD POLAR MOLECULES SPECTROSCOPY ROTATIONAL SPECTROSCOPY OF SYN AND ANTI-CLINAL PENTA-3,4-DIENENITRILE FROM 130-375 GHz TING GONG, State Key Laboratory of Quantum Optics and Quantum Optics Devices, Institute of Laser Spec- VANESSA L. ORR, BRIAN J. ESSELMAN, ANDREW N OWEN, SAMUEL M. KOUGIAS, R. CLAUDE troscopy, Shanxi University, Taiyuan, Shanxi, China; ZHONGHAO LI, School of Instrument and Electron- WOODS, ROBERT J. McMAHON, Department of Chemistry, University of Wisconsin, Madison, WI, USA. ics, North University of China, Taiyuan, Shanxi, China; ZHONGHUA JI, YANTING ZHAO, YUTING LIU, LIANTUAN XIAO, SUOTANG JIA, State Key Laboratory of Quantum Optics and Quantum Optics Devices, Penta-3,4-dienenitrile, (P34DN, H2C=C=CHCH2CN), is an intriguing target for detection in the interstellar medium and the atmosphere of Titan because of its structural similarity to known interstellar molecules and because it is a constitutional Institute of Laser Spectroscopy, Shanxi University, Taiyuan, Shanxi, China. isomer of the simple aromatic compound, pyridine (c-C5H5N). P34DN has recently been synthesized in our group and its The high-resolution microwave (MW) spectroscopy is employed to measure the rotational structures of ultracold millimeter-wave spectrum has been collected from ∼130-375 GHz. Computational studies reveal that P34DN has two stable 85 133 1 + Rb Cs molecules prepared in the X Σ (v = 0) ground state. These ground-state molecules are created using short-range conformers linked by the internal rotation of the −CH2CN group and separated by <1 kcal/mol. The internal rotation is the photoassociation (PA) followed by the spontaneous emission. Using a combination of continuous-wave (CW) depletion spec- lowest fundamental, ν27, in both conformers. Over 800 distinct rotational transitions of the ground vibrational state of the troscopy and photoionization (PI) technique, we obtain the MW spectroscopy by coupling the neighboring rotational levels syn conformer (C , μ =1.7 D, μ =3.1 D, CCSD(T)/cc-pVTZ) have been least-squares fit to a single-state centrifugally s a b of ground-state molecules. Based on the frequency spacing obtained from the MW spectroscopy, the rotational constant of distorted rotor model using Kisiel’s ASFIT, and analysis of this ground state is ongoing. 1 + X Σ (v = 0) can be accurately determined with the rigid rotor model. The precision of the measurement by MW spec- The anti-clinal conformer of P34DN has C1 symmetry (μ =3.4 D, μ =1.9 D, μ =0.6 D, CCSD(T)/cc-pVTZ). a b c troscopy is found to be 3 orders of magnitude higher than the CW depletion spectroscopy. Our scheme provides a simple and Rotational transitions for the ground state and the vibrational states ν27, 2ν27, 3ν27,and4ν27 have been identified. Clear −1 highly accurate method for the measurement of molecular structure. evidence of strong Coriolis coupling between the ground state and ν27 (∼ 52 cm ) has been observed, primarily between K =18of the ground state and K =14of the excited state. Coupling is also observed between the v = 1 and v = 2 of ν27. This presentation will discuss the current analysis of the coupling between the ground state and ν27 v = 1 and the current status of their coupled least-squares fit using Pickett’s SPFIT program. 200 201 RJ. Atmospheric science RJ03 2:21 – 2:36 Thursday, June 20, 2019 – 1:45 PM INVESTIGATION OF REFERENCE SPECTROSCOPIC PARAMETERS OF WATER VAPOR IN APPLICATION TO AT- MOSPHERIC OBSERVATIONS IN THE 22 230 - 22 721 cm−1 REGION Room: 217 Noyes Laboratory EAMON K CONWAY, Atomic and Molecular Physics , Harvard-Smithsonian Center for Astrophysics, Cam- Chair: Zachary Reed, National Institute of Standards and Technology, Gaithersburg, MD, USA bridge, MA, USA; IOULI E GORDON, KELLY CHANCE, Atomic and Molecular Physics, Harvard-Smithsonian Center for Astrophysics, Cambridge, MA, USA; JONATHAN TENNYSON, Department of Physics and Astron- omy, University College London, Gower Street, London WC1E 6BT, United Kingdom.

16 −1 An analysis of theoretical and experimental H2 O line shape parameters and line intensities in the 22 230 - 22 721 cm window is presented. This visible region is often used in the retrieval of water vapor in the terrestrial atmosphere as there is minimum interference from other molecules and it is therefore vital to have highly accurate water parameters available. The HITRAN2016 database (Gordon et al. (2017)) is an important resource for performing such retrievals and for 16 H2 O, the visible section of the database contains data from numerous sources, both theoretical and experimental. We compute two sets of cross sections, one using only theoretical sources, the other using data only from HITRAN2016. Both RJ01 1:45 – 2:00 sets are compared to the cross-sections generated based on the atmospheric observation of this visible region by Harder et al. THE ATMOSPHERIC CHEMISTRY EXPERIMENT (ACE) SATELLITE: NEW PROCESSING RESULTS (1997). Neither set modeled the entire observed spectrum better than the other, however, each set did provide lower residuals than the other for particular regions. PETER F. BERNATH, Department of Chemistry and Biochemistry, Old Dominion University, Norfolk, VA, USA; Despite using only approximate broadening parameters in the first set of theoretical cross sections, an inter-comparison CHRIS BOONE, Department of Chemistry, University of Waterloo, Waterloo, ON, Canada. with HITRAN2016 allowed us to identify in-accurate broadening parameters from a common source. This region of HI- TRAN2016 combines both the theoretical intensities of Barber and Tennyson (2006), also known as BT2, with experimental After almost 16 years in low-Earth orbit, the ACE satellite (aka SCISAT) is making near-real time measurements of measurements of Tolchenov et al. (2005). Inconsistencies between the theoretical line intensities were clearly apparent. Re- numerous trace gases, thin clouds, aerosols and temperature by solar occultation. A high inclination orbit gives coverage of placing both the incorrect line shape parameters and line intensities with values from alternative sources or estimated using tropical, mid-latitude and polar regions. The primary instrument is a high-resolution (0.02 cm−1) infrared Fourier transform different approaches has improved the overall residual on the HITRAN cross sections. This will be important for the future spectrometer (FTS) operating in the 750–4400 cm−1 region, which provides data for the vertical distribution of trace gases, retrievals of atmospheric water vapor. and for temperature and pressure. Aerosols and clouds are monitored by their infrared spectra and through the extinction of solar radiation using two filtered imagers. Our new version of FTS processing, v.4.0, retrieves 44 molecules including 19 halogen-containing gases, in addition to 24 isotopologues, and features new routine data products SO2, ClO, HFC-134a, HFC-23, acetone, acetonitrile, PAN (peroxy- acetyl nitrate) and low altitude CO2. At low altitudes (5.5 to 17.5 km) collision-induced absorption spectra of nitrogen provide the pointing (tangent altitude of the field-of-view). When combined with the Canadian weather service model, the pointing yields our new low altitude CO2 data product. ACE monitors the Montreal Protocol substances that deplete the ozone layer, and all of the main greenhouse gases, including CO2, responsible for climate change. See http://www.ace.uwaterloo.ca for more information.

RJ04 2:39 – 2:54 HIGH ACCURACY LINE INTENSITIES FOR NEAR-INFRARED CARBON DIOXIDE BANDS

DAVID A. LONG, ZACHARY REED, ADAM J. FLEISHER, ERIN M. ADKINS, Material Measurement Lab- oratory, National Institute of Standards and Technology, Gaithersburg, MD, USA; HONGMING YI, Department of Civil and Environmental Engineering, Princeton University, Princeton, NJ, USA; HELENE M FLEURBAEY, Material Measurement Laboratory, National Institute of Standards and Technology, Gaithersburg, MD, USA; RJ02 2:03 – 2:18 JOSEPH MENDONCA, Environment and Climate Change Canada, Toronto, Canada; JOSEPH T. HODGES, OZONE ISOTOPOLOGUE MEASUREMENTS FROM THE ATMOSPHERIC CHEMISTRY EXPERIMENT (ACE) Material Measurement Laboratory, National Institute of Standards and Technology, Gaithersburg, MD, USA.

ANTON MADUSHANKA FERNANDO, Department of Physics, Old Dominion University, Norfolk, VA, USA; The near-infrared bands of carbon dioxide (CO2) play an important role in point source as well as remote sensing PETER F. BERNATH, Department of Chemistry and Biochemistry, Old Dominion University, Norfolk, VA, USA; measurements. Here we have measured high accuracy line intensities for the (30012)←(00001), (30013)←(00001), and CHRIS BOONE, Department of Chemistry, University of Waterloo, Waterloo, ON, Canada. (30014)←(00001) bands near 1.6 μm. Three separate cavity ring-down spectrometers were employed: a frequency-agile, rapid scanning spectrometer and two frequency-stabilized spectrometers. Through this combination of instruments, we have Near global ozone isotopologue distributions have been determined from infrared solar occultation measurements of the reached relative combined standard uncertainties as low as 0.1% for the band intensities. I will discuss these measurements Atmospheric Chemistry Experiment (ACE) satellite mission. ACE measurements are made with a high resolution Fourier as well as comparisons to existing spectroscopic models and databases. Finally, I will present the results of atmospheric transform spectrometer. Annual and seasonal latitudinal fractionation (δ value) distributions of the ozone isotopologues retrievals using these line intensities. 16O16O18O, 16O18O16Oand16O17O16O were obtained. Asymmetric ozone (16O16O18O) shows higher fractionation com- pared to symmetric ozone (16O18O16O). The maximum ozone fractionation occurs in the tropical stratosphere as expected. An enhancement of the heavy ozone isotopologues is also seen in the Antarctic polar vortex.

Intermission 202 203

RJ05 3:33 – 3:48 RJ07 4:09 – 4:24 CRIEGEE INTERMEDIATES REACTIONS WITH FORMIC ACID PROBED BY FTMW SPECTROSCOPY THE REACTION OF CH2OO WITH HNO3 INVESTIGATED WITH A STEP-SCAN FTIR SPECTROMETER

CARLOS CABEZAS, Instituto de Fisica Fundamental, CSIC, Madrid, Spain; YASUKI ENDO, Department of CHEN-AN CHUNG, CHO-WEI HSU, YUAN-PERN LEE, Department of Applied Chemistry, National Chiao Applied Chemistry, National Chiao Tung University, Hsinchu, Taiwan. Tung University, Hsinchu, Taiwan.

Gas-phase ozonolysis is a major degradation mechanism of alkenes in the Earth’s atmosphere and forms Criegee in- Carbonyl oxides, which are known as Criegee intermediates, are important intermediates produced in ozonolysis of un- a termediates (CIs), carbonyl oxides, as reactive intermediates. The chemistry of CIs plays a central role in controlling the saturated hydrocarbons. Criegee intermediates react readily with other atmospheric species such as HNO3, SO2,(H2O)2 budgets of many tropospheric species including OH, organic acids, and secondary organic aerosols (SOA). The reaction of and HCOOH, leading to production of OH, aerosols and organic acids in the atmosphere. The reaction coefficient between −10 3 −1 −1 b CIs with organic acids can provide a pathway in which alkenes are converted to low-volatility compounds and thus con- CH2OO and HNO3 was reported to be 5.4×10 cm molecule s at 298 K. Theoretical calculations also predict a tribute to the formation of SOA. Here we report spectroscopic investigation, through pure rotational spectroscopy, of the similar rate coefficient for CH2OO + HNO3, the reaction goes through a barrierless path to form nitrooxymethyl hydroper- −1 reaction between the simplest Criegee intermediate, CH2OO, and the simplest organic acid, the formic acid, HCOOH. In this oxide (NMHP, NO3CH2OOH). Besides, due to large exothermicity(-184.9 kJ mol ), internally excited NMHP might c experiment, CH2OO molecules have been generated in the discharged plasma of a CH2I2/O2 mixture, which containing a decompose further to CH2ONO3 and OH. small amount of HCOOH enough to react with CH2OO. The resulting products (including CH2OO) were characterized by In this work, we utilized a step-scan FTIR coupled with a multipass White cell to record time-resolved IR absorption Fourier-transform microwave (FTMW) spectroscopy. Rotational transitions in the 6-40 GHz frequency range were observed spectra of the reactants and products during the reaction of CH2OO with HNO3 in a flow system with total pressure about by FTMW spectroscopy together with MW-mmW and MW-MW double-resonance techniques. Preliminary results for the 10 Torr. CH2OO was produced from the reaction of CH2I + O2; CH2I was produced from photolysis of CH2I2 at 308 −1 reaction of both conformers of the methyl-substituted Criegee intermediate, CH3CHOO, with formic acid are also presented. nm.d The IR absorption spectra were recorded at instrumental resolution 0.3 cm . Newly observed bands at 825, 967, 1053, 1294, 1348, 1424, 1686 and 3587 cm−1can be assigned to NMHP. The observed wavenumbers and relative intensities agree with the anharmonic vibrational wavenumbers and IR intensities predicted with the B3LYP/aug-cc-pVTZ method. In addition, we also observed several bands with clear rotational structure, which can be assigned to the absorption of NO2, H2CO and HO2. Observation of these species indicates that another decomposition route for excited NMHP might exist. Furthermore, absorption bands of unternally excited HNO3 was also observed at low pressure, indicating that decomposition of pre-reaction complex can excite HNO3. By probing the formation of NMHP and NO2, the rate coefficient of this reaction was determined to be (5.3±0.8)×10−10 cm3 molecule−1 s−1.

aR. Criegee, Angew. Chem. Int. Edit. 14, 745 (1975). bE. S. Foreman, K. M. Kapnas and C. Murray, Angew. Chem. Int. Edit. 55, 10419 (2016). cP. Raghunath, Y. P. Lee and M. C. Lin, J. Phys. Chem. A 121, 3871 (2017). dO. Welz, J. D. Savee, D. L. Osborn, S. S. Vasu,C. J. Percival, D. E. Shallcross and C. A. Taatjes, Science 335, 204 (2012).

RJ08 4:27 – 4:42 INELASTIC COLLISION DYNAMICS OF O3+Ar RJ06 3:51 – 4:06 FTMW SPECTROSCOPY OF THE METHYL-VINYL CRIEGEE INTERMEDIATE SANGEETA SUR, STEVE ALEXANDRE NDENGUE, ERNESTO QUINTAS SANCHEZ,´ RICHARD DAWES, Department of Chemistry, Missouri University of Science and Technology, Rolla, MO, USA. YASUKI ENDO, CHEN-AN CHUNG, YUAN-PERN LEE, Department of Applied Chemistry, National Chiao Tung University, Hsinchu, Taiwan. Collisional energy transfer between a metastable ozone molecule and an inert collider such as an argon atom is a key step in the formation process of ozone. Understanding these collisional cooling dynamics may provide insight into the “ozone Pure rotational transitions of the methyl-vinyl Ciregee intermediate have been observed by FTMW spectroscopy. The isotopic anomaly”, which is the observation of larger than expected concentrations of certain heavy ozone isotopologues in species was produced by discharging a mixture, 1,3-diiodo-but-2-en and O2 diluted in Ar. Among four possible isomers the atmosphere. Although many explanations to understand this phenomenon have been put forward previously, quantita- for this species with energy less than 3 kcal/mol, only the lowest energy isomer, the syn-trans isomer was detected. Thirty tive prediction/understanding is still lacking. One of the major reasons is the lack of an accurate potential energy surface rotational transitions with internal rotation splitting for the methyl top were observed. The observed frequencies were analyzed 3 + 1 (PES) for the system. We have recently constructed a new and accurate DPESofO3 Ar and computed bound states of by the XIAM program, yielding the rotational constants, which agree very well for the lowest energy isomer, giving definite the complex within the rigid rotor approximation.a In this work, we now present the dynamics of collisions between this assignment of the isomer observed. Furthermore, the internal rotation barrier was determined to be 702.8(28) cm−1, which −1 triatomic asymmetric top molecule and a heavy atom: O3–Ar. The MultiConfiguration Time Dependent Hartree (MCTDH) also reasonably agrees with that of an ab initio calculation 680 cm at CCSD(T)/cc-pVTZ. method was used to study the scattering between the O3 molecule and Ar atom. The state-to-state probabilities from the 000 rotational state to low lying excited rotational states as well as the state-to-state cross sections are determined for the system. 1. H. Hartwig and H. Dreizler, Z. Narturforsch. A 51, 923 (1996). 16 16 16 16 16 18 The rate coefficients obtained for O O O–Ar, are compared with the rate coefficients obtained for the O O O–Ar isotopologue. The lowered symmetry in 16O16O18O–Ar results in roughly double the density of allowed states due to nuclear spin statistics for bosons, which impacts the scattering dynamics.

a S. Sur, E. Quintas-Sanchez,´ S. A. Ndengue,´ R. Dawes ”Development of a potential energy surface for the O3–Ar system: Rovibrational states of the complex”, Submitted, PCCP (2019) 204 205 RK. Mini-symposium: High-Harmonic Generation and XUV Spectroscopy RJ09 4:45 – 5:00 Thursday, June 20, 2019 – 1:45 PM RADIATIVE CHARGE TRANSFER AND ASSOCIATION IN Ar+H+ AND Ar++H COLLISIONS Room: B102 Chemical and Life Sciences M. BOULEDROUA, Departement´ de Medecine,´ FacultedeM´ edecince´ & L.P.R., Annaba, Annaba, Algeria; FATIMA TALHI, Physics Department, Badji Mokhtar University, Annaba, Annaba, Algeria. Chair: Scott G Sayres, Arizona State University, Tempe, AZ, USA

A 2013 paper by Barlow et al.a revealed the presence of argonium 36ArH+ in the Crab Nebula by detecting the rotational lines J=1-0 and J=2-1 at the frequencies 617.53 and 1234.60 GHz, respectively. The finding was the first noble gas molecule detected in space. Since then, this astrophysical discovery launched a great amount of investigations dealing with the ionic dimer ArH+. b + + The present work aims at the characterization of two argonium isotopologues, namely, 36ArH and 38ArH ,bylooking RK01 INVITED TALK 1:45 – 2:15 at the radiative processes of charge transfer (1) and association (2): + 2 2 1 + TOWARD ATTO-PUMP-ATTO-PROBE SPECTROSCOPY OF ELECTRONIC DYNAMICS Ar ( P) + H( S) → Ar( S) + H +hν (1) 1,3 + → + Ar( P) + H ArH +hν.(2) WEN LI, Department of Chemistry, Wayne State University, Detroit, MI, USA. To accomplish these two tasks, the corresponding potential-energy curves and transition dipole moments are determined 1 + 1 + 1 1 + 1 in order to construct the ground X Σ and excited A Σ ,B Π,C Σ ,andD Π molecular states and the allowed transition Attosecond spectroscopy promises a real-time probe of electronic dynamics, such as those involved in nonsequential moments that connect the ground and excited singlet states, i.e., A → X, B → X, C → X, and D → X. Once all the required two-photon double ionization (NSDI) and charge migration driven by electron correlation and electronic relaxation. A XUV- + ArH curves are well established and their physical features and spectroscopic values are contrasted with previous published pump-XUV-probe setup is considered a general method for implementing attosecond spectroscopy, similar to the pump-probe + data, the cross sections, for the radiative charge transfer in the Ar +H collisions and for the formation of the diatomic ions scheme that has been successfully applied in femtosecond spectroscopy. However, major technical issues need to be solved + ArH by radiative association, are computed quantum-mechanically at lower and higher energies. Finally, the temperature- in order to carry out such experiments in attosecond time-domain. dependent rate coefficients are calculated, and the numerical results are discussed and fitted to a selected analytical expression. In this talk I will discuss our effort in developing such techniques through two different routes: 1) intense high harmonic

aM.J. Barlow et al., Science 342, 1343 (2013). generation and 2) attosecond angular streaking. In the first approach, we achieved ion-electron coincidence detection of two- bM. Cueto et al., Astrophys. J. Lett. 783, L5 (2014). P. Schilke et al., Astron. Astrophys. 566, A29 (2014). E. Roueff et al., Astron. Astrophys. 566, A30 (2014). H.S.P. Muller¨ photon double ionization of an atomic system using intense XUV pulses produced through high harmonic generation. In the et al., Astron. Astrophys. 582, L4 (2015). J.A. Coxon and P.G. Hajigeorgiou, J. Mol. Spectrosc. 330, 63 (2016). L. Bizzocchi, Astrophys. J. Lett. 820, L26 (2016). F.D. Priestley second approach, employing a novel attosecond angular streaking technique, we probed electron dynamics taking place in et al., Mon. Not. Roy. Astron. Soc. 472, 4444 (2017). the first 500 attoseconds after pumping. These techniques will ultimately bring time-resolved spectroscopy to the attosecond domain.

RK02 2:21 – 2:36 MACROSCOPIC SIMULATION OF NEAR-THRESHOLD HIGH HARMONIC GENERATION USING MICROSCOPIC TDSE/TDDFT CALCULATIONS

RREIFF, J VENZKE, T JOYCE, ANDREAS BECKER, AGNIESZKA JARON-BECKER, JILA and Depart- ment of Physics, University of Colorado, Boulder, CO, USA.

Modelling strong-field induced radiation near the ionization threshold requires careful treatment of excited state dynamics. So- 15 lution of the time dependent Schrodinger equation (TDSE) pro- -5.5 13 vides accurate data in this regime, but the computational time -6

needed prohibits direct calculation of the macroscopic response 11 -6.5 (e.g., from a gas jet) due to the range of intensities to be consid- ered. We apply a method of interpolation of (precalculated) TDSE 9 -7

-7.5 results as a function of laser intensity at a given wavelength to 7 Harmonic (0.057a.u.) simulate the macroscopic propagation of the high harmonic sig- -8 nals using the discrete dipole approximation. This allows inves- 5 -0.015 -0.01 -0.005 0 0.005 0.01 0.015 tigation of the angular dependence of harmonic and off-harmonic Detector Angle (rad) radiation near and below the ionization threshold (see Fig. 1). The method can be extended beyond the hydrogen atom through the Figure 1: Angle-resolved high-order harmonic spectrum Single Active Electron (SAE) approximation or Time Dependent from 5 × 105 hydrogen atoms. Note the difference in Density Functional Theory (TDDFT). Results for the helium atom structure of harmonic peaks versus off-harmonic lines + (SAE) and N2 molecule (TDDFT) will be presented. This work was supported by AFOSR MURI (Grant No. FA9550-16-1-0121) and DOE-BES (Award No. DE-SC0001771) 206 207

RK03 2:39 – 2:54 RK05 3:51 – 4:06 IDENTIFYING THE TRIPLET INTERMEDIATE STATE IN THE ULTRAFAST PHOTOINDUCED SPIN-TRANSITION PHOTOINDUCED RING CURRENTS IN MOLECULES OF LOW-SPIN IRON(II) COMPOUNDS USING FEMTOSECOND M2,3-EDGE ABSORPTION SPECTROSCOPY AGNIESZKA JARON-BECKER,TJOYCE,JILA and Department of Physics, University of Colorado, Boulder, KAILI ZHANG, Department of Chemistry, University of Illinois at Urbana-Champaign, Urbana, IL, USA; CO, USA. RYAN T ASH, Chemistry, University of Illinois at Urbana-Champaign, URBANA-CHAMPAIGN, IL, USA; ELIZ- ABETH S RYLAND, KRISTOPHER BENKE, MAX A VERKAMP, Department of Chemistry, University of Circularly polarized laser pulse can induce electronic ring currents within a single molecule, that are expected to persist Illinois at Urbana-Champaign, Urbana, IL, USA; MING-FU LIN, Stanford Synchrotron Radiation Lightsource, for as long as nanoseconds. Photoinduced ring currents in molecules have not yet been observed experimentally, and most 12 2 SLAC National Accelerator Laboratory, Menlo Park, CA, USA; FRANK DE GROOT, Department of Chemistry, theoretical studies have considered rather weak laser intensity - below 10 W/cm , which limits the strength of the induced Utrecht University, Utrecht, The Netherlands; GREGORY S. GIROLAMI, JOSH VURA-WEIS, Department of current. Chemistry, University of Illinois at Urbana-Champaign, Urbana, IL, USA. We study the properties of the ring current that can be in- duced in benzene, over the range of laser pulse frequencies and In this work, we perform femtosecond M2,3-edge XANES on low-spin iron complexes using a high harmonic generation intensities. Simulations within Time-Dependent Density Func- (HHG) light source. Low-spin iron complexes hold promise as affordable alternatives to ruthenium-based photosensitizers. tional Theory (TDDFT) are compared to results obtained within Conventional iron complexes with polypyridyl ligands are unsuitable because the excitation energy is dissipated in 200 fs by Tight Binding method. In the regime of the excitation of the per- ultrafast population of the low-lying quintet metastable state. This formally ΔS=2 process is conjectured to proceed through sistent ring current one can observe influence of the resonance a metal-centered triplet intermediate state, but spectroscopic evidence of such an intermediate has remained elusive. Here enhanced ionization (REMPI) on the current. we use femtosecond M2,3-edge XANES to elucidate the role of metal-centered intermediate states. The transient response Our results indicate that circularly-polarized femtosecond 3 of Fe(phen)3(SCN)2 following excitation in the MLCT band clearly shows the presence of a metal-centered T1 state. The laser pulse can be used to control ionization and efficient ioniza- transient response also shows oscillations consistent with the evolution of a vibrational wave-packet on the quintet surface. We tion leads to a persistent hole current. Consequently for higher also recorded the M2,3-edge transient response of Fe[(CF3)2bpca]2, a complex with a weaker ligand field. A comparison of intensities of the laser pulse the leading contribution from the the photophysical behaviors of Fe(phen)3(SCN)2 and Fe[(CF3)2bpca]2 sheds light on the influence of crystal field strength on hole current induces the change of the direction of the total ring the relaxation mechanism of the MLCT state. Our findings add a hitherto missing piece to the existing picture of photophysics current (see Figure 1). Furthermore we present how the mech- of iron complexes. anism can be used to switch between the two regimes of co- Figure 1: Induced current as a function of the peak laser and counter propagating ring currents during the laser pulse and intensity. Tight binding method (dashed red line) versus discuss properties of ring currents in other molecules. TDDFT (solid blue line) results.

RK04 2:57 – 3:12 A VELOCITY MAP IMAGING ANALYSIS OF Fe(CO)5, W(CO)6 AND ELECTRON STIMULATED DESORPTION IN Me2Au(acac)

MARIA PINTEA,NIGELMASON,School of Physical Sciences, Kent University, Canterbury, United Kingdom; LIONEL AMIAUD, Institut des Sciences Moleculaires´ d’Orsay, Universite´ Paris-Sud, Orsay, France. RK06 4:09 – 4:24 COINCIDENCE MEASUREMENTS OF STRONG FIELD MOLECULAR DOUBLE IONIZATION Tungsten hexacarbonyl and iron pentacarbonyl are two of the common precursors used for Focused Electron Beam Induced Deposition (FEBID). FEBIP is one of the new techniques explored by the nanotechnology industry to build sub- CHUAN CHENG, Department of Physics, Stony Brook University, Stony Brook, NY, USA; PATRICIA VINDEL 10nm structures. Velocity Map Imaging (VMI) technique has been used in the study of the Fe(CO)5 and W(CO)6 compounds ZANDBERGEN, SPIRIDOULA MATSIKA, Department of Chemistry, Temple University, Philadelphia, PA, to refining Malli L. Gulzari et al. [3], Rosenberg G. et al. [4] the electron beam induced deposition process by giving the USA;THOMASWEINACHT,Department of Physics, Stony Brook University, Stony Brook, NY, USA. essential details on this molecules, such as cross sections, kinetic energies, angular distributions. Neustetter M. et al. [5], Thon R. et al. [6] Double ionization has been well studied in atoms and diatomic molecules. However, polyatomic molecules, with more A molecular analysis of surfaces and deposition of Me2Au(acac) has been performed using electron stimulated desorption complicated electronic structure, have not been studied as extensively. (ESD) and temperature programmed desorption (TPD) revealing the presence of C2H2, AuII, CO, O+. A plain Copper We use few cycle intense ultrafast laser pulses and coincidence velocity map imaging to investigate strong field double substrate has been used for deposition of the compound at a pressure of 10-8 mbar for 2 min, equivalent to 3.4L. ionization in molecules such as CH2IBr and 1,3-Cyclohexadiene. By using a time stamping camera to make vector momentum This work is part of the ELENA Horizon 2020 Training Network, www.elena-eu.org was developed as a European measurements of electrons and ions, we are able to distinguish between multiple double ionization channels. Different double Initiative to support the emerging nanotechnology market and as a response to the increasing demand in this field. ionization channels which result in different fragment ion pairs show different electron correlation patterns, indicating that the double ionization dynamics are influenced by the orbitals from which the electrons are removed.

Intermission 208 209 RL. Spectroscopy as an analytical tool Thursday, June 20, 2019 – 1:45 PM RK07 4:27 – 4:42 Room: 2079 Natural History PROBING THE ULTRAFAST INTERMEDIATE STATES OF A DIVALENTCO-MN COMPLEX WITH FEMTOSECOND M-EDGE XANES Chair: Neil J Reilly, University of Massachusetts Boston, Boston, MA, USA

ELIZABETH S RYLAND, KAILI ZHANG, CLARE LEAHY, JOSH VURA-WEIS, Department of Chemistry, RL01 1:45 – 2:00 University of Illinois at Urbana-Champaign, Urbana, IL, USA. STUDY OF STRENGTH VARIATIONS IN STEROIDS USING LIBS

In this work we perform ultrafast transient M2,3-edge XANES on divalent cobalt-manganese(N,N,N-tri(2-(2- pyridylamino)ethyl)amine)Cl, a heterobimetallic system with directly-interacting dual metal centers held within a non- P. K. TIWARI,A.K.RAI,Department of Physics, Allahabad University, Allahabad, India. innocent ligand scaffold. The strong metal-metal interaction facilitated by the ‘double-decker’ type ligand scaffold leads In the present scenario, a number of approaches are available for the elemental analysis of drug samples but quick to a highly multiconfigurational electronic structure with relaxation pathways unavailable in monometallic analogues. With and cost-effective techniques are vital in the drug manufacturing industry. During the last few decades, Laser Produced the ultrashort broadband probe pulse used in transient high-harmonic generation spectroscopy, we are able to perform M2 3- , Plasma which is also known as Laser Induced Breakdown Spectroscopy (LIBS) has been adopted as a viable spectroscopic edge XANES on both metal edges simultaneously with high specificity for each metal center and ligand environment. By analytical technique in the various field. In the pharmaceutical arena, a wide range of applications including the analysis of combining transient XANES with transient UV-visible spectroscopy we have compiled a full picture of the electronic relax- the active pharmaceutical ingredients (API) and excipients etc., the utility of LIBS have begun to emerge. The steroids of ation dynamics of this complex molecule. Photoinduced MM’CT is followed by distinct electronic dynamics at both metal different brand and dosages have been taken for the analysis. LIBS is basically atomic spectroscopic technique however, in edges and within the ligand scaffold, suggesting complex interplay of the Co, Mn, and ligand redox centers. Increased under- the present approach, molecular signatures of the drug sample were also investigated using LIBS and being conformed to the standing of the relation of function to metal-specific photodynamics will help lay essential groundwork for the development complementary techniques i.e. Raman and FTIR spectroscopy. of multimetallic catalysts with efficiencies comparable to those found in nature.

RL02 2:03 – 2:18 RK08 4:45 – 5:00 STUDY OF ELEMENTAL AND MOLECULAR EVIDENCES IN DRUGS USING LIBS IMAGING OF ATTOSECOND RING CURRENT DYNAMICS A. K. RAI,P.K.TIWARI,Department of Physics, Allahabad University, Allahabad, India. JVENZKE, JILA and Department of Physics, University of Colorado, Boulder, CO, USA; CORY GOLD- SMITH, JILA and Department of Chemistry, University of Colorado, Boulder, CO, USA; AGNIESZKA JARON- Laser Induced Breakdown Spectroscopy (LIBS) spectra of some WHO listed essential pharmaceutical drugs have been BECKER, ANDREAS BECKER, JILA and Department of Physics, University of Colorado, Boulder, CO, USA. recorded in air and argon atmosphere. The spectral signatures of characteristic molecular emission of the CN violet band system and C2 Swan band system along with the atomic and ionic lines of various elements are observed in the LIBS spectra When a helium atom is excited into a superposition of a of the drug samples. We have measured the intensity of these molecular bands. With the help of the intensities of these bands, 1s state and a np+ state, the electron wave packet produces an attempt has been made to correlate the CN violet and C2 swan band with the chemical structure of the molecule present a ring current with attosecond scale charge density dynam- in the drugs. The essential drugs of different brands have been taken for the LIBS analysis. PCA (a multivariate method) ics. The dynamics in the field free wave packet manifest has also been applied on the LIBS dataset for the discrimination purpose of the drugs which have a similar composition. In in a time dependent relative phase between the ground and addition to this, for the confirmation of the molecules present in the drug, complementary molecular spectroscopic techniques, excited state. In this talk, we will discuss an interference called Raman and FT-IR spectroscopy, have been applied to find out the molecular spectra of these drug samples. With scheme that allows for time resolved imaging of the relative the implementation of the above approach, it is established that LIBS techniques may be used as an online drugs analysis phase of the bound states to be extracted from a photoelec- technique in pharmaceutical industries. tron spectrum. The presented results are obtained from ab initio simulations of the time dependent Schrodinger¨ equa- RL03 2:21 – 2:36 tion in the single active electron and dipole approximations. BASELINE-FREE MEASUREMENT OF TEMPERATURE, PRESSURE, AND CONCENTRATION FROM MOLECU- Effects of pulse length, polarization and other parameters of Figure 1: Photoelectron spectra of He atom in a superposition LAR FREE INDUCTION DECAY the imaging pulse on the obtained data will be discussed. of 1s and a 2p+ with different initial relative phase. This work was supported by DOE-BES (Award No. RYAN K. COLE, AMANDA S. MAKOWIECKI, NAZANIN HOGHOOGHI, GREGORY B RIEKER, Depart- DE-SC0001771) and NSF JILA Physics Frontier Center (Grant No. PHY 1734006) ment of Mechanical Engineering, University of Colorado Boulder, Boulder, CO, USA.

Broadband laser absorption spectrometers have enabled sensing of temperature, pressure and absorber mole fraction in gaseous systems with high sensitivity and precision. However, recovering thermodynamic conditions from the measured spectrum can be complicated by the need to correct for the background intensity spectrum of the laser source (the ‘base- line’). Baseline correction becomes challenging for highly modulated laser spectra (e.g. from non-linear spectral broadening processes or etalon effects in the optical system) as well as in the presence of broadband absorption from large molecules (e.g. hydrocarbons). In this talk, we demonstrate a technique for measuring temperature, pressure, and species concentration from an absorption spectrum without the need to correct for the laser intensity spectrum. This technique is based on the time domain description of absorption spectroscopy – where the typical absorption features manifest as the temporal dynamics of the excited molecules. We demonstrate the fitting technique by accurately measuring temperature and pressure from the broadband spectrum of water vapor over a range exceeding 1000 K. Further, we apply the technique to a broadly absorbing mixture by accurately recovering species concentrations from a mixture of ethane and methane. This mixture absorbs contin- uously for more than 500 cm−1 in the near-infrared, and thus poses a significant challenge for traditional baseline correction methods. By eliminating the need to correct for the laser intensity spectrum, our results address a significant limitation of broadband laser absorption spectroscopy for sensing applications. 210 211

RL04 2:39 – 2:54 RL06 3:15 – 3:30 HIGH RESOLUTION COHERENT 2D AND 3D SPECTROSCOPY NEAR-INFRARED MOLECULAR SPECTROSCOPY USING NICE-OHMS WITH HIGH FINESSE CAVITY

PETER CHEN, THRESA WELLS, Department of Chemistry, Spelman College, Atlanta, GA, USA. TZULING CHEN, Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, CA, USA; YIWEI LIU, Department of Physics, National Tsing Hua University, Hsinchu, Taiwan. High resolution coherent multidimensional spectroscopy is a powerful new tool that can be used to overcome difficulties encountered with other forms of spectroscopy. The 2D spectra have reduced congestion and show easily recognizable patterns, Noise-immune cavity-enhanced optical heterodyne molecular spectroscopy (NICE-OHMS), taking advantage of com- even for molecules that yield patternless 1D spectra Furthermore, the peaks are automatically sorted by quantum number and bining the cavity enhancement and frequency modulation techniques, provides an excellent method to enable ultra sensitive species. The 3D technique further reduces congestion, provides selectivity, and can be used to generate unique 3D rotational detection. The advantage of noise immunity enables for shot-noise limit detection, particularly for those molecules with ultra- patterns. This talk provides an overview of newly developed high resolution coherent 2D and 3D techniques. small dipole moments, such as overtone transitions and symmetrical molecules, NICE-OHMS provides a superior strategy to achieve sub-Doppler saturation spectroscopy. Using an optical cavity with a high finesse >100,000, in our previous work, we reported the sub-Doppler saturation NICE-OHMS spectroscopy for nitrous oxide (N2O) overtone transitions using the quantum-dot (QD) laser developed at 1.28 μm. At a pressure of several mTorr, the saturation dip is observed with a full width at half-maximum of about 2 MHz. The noise equivalent bandwidth-reduced sensitivity is 1.6×10−11cm−1Hz−1/2.TheQD laser is then locked to this dispersion signal with a stability of 15 kHz at 1 s integration time. We demonstrate the potential of the (N2O) as a marker because of its particularly rich spectrum in the vicinity of 1.28 μm, where there are several important forbidden transitions of atomic parity violation measurements. In current work, we have used a new QD laser system coupled to a high finesse cavity for NICE-OHMS of the H2 overtone transition S1, where the dipole moment is only 30 mD. The QD laser developed at 1.16 μm is gain-chip based and mounted in an integrated mechanism system to reduce the passive laser linewidth. The cavity finesse was measured to be 234,000 (8000) by using laser-swept cavity ring-down time measure- ments. After the laser locking, the laser power will be amplified by a fiber amplifier to satisfy saturation condition to achieve sub-Doppler NICE-OHMS spectroscopy.

RL05 2:57 – 3:12 IMPLICATIONS OF SELF-PHASE MODULATION (SPM) FOR N2 FEMTOSECOND COHERENT ANTI-STOKES RA- MAN SCATTERING (FS CARS) SPECTROSCOPY AT ELEVATED PRESSURE

MINGMING GU, Department of Mechanical Engineering, Purdue University, West Lafayette, IN, USA;AMAN SATIJA, ROBERT P. LUCHT, Mechanical Engineering, Purdue University, West Lafayette, IN, USA. Intermission

Femtosecond coherent anti-Stokes Raman scattering (fs-CARS) is a non-linear spectroscopic technique that has been widely used in var- 1.0 1 bar ious combustion related environments to measure the temperature and 4 bar species concentration information. On the other hand, self-phase mod- 7 bar RL07 4:09 – 4:24 0.5 ulation (SPM) describes a Kerr-like effect in which an ultrashort pulse MOLECULAR COMPOSITION OF GALLBLADDER STONE USING PHOTOACOUSTIC SPECTROSCOPY accumulates nonlinear phase as it propagates through the gas medium N2 CH4 Intensity (a.u.) like N2. As a result, the application of fs-CARS in the high pressure envi- 0.0 A. K. RAI, ZAINAB GAZALI, P. K. TIWARI, Department of Physics, Allahabad University, Allahabad, India; ronment will inevitably need to deal with SPM influence especially when 1.0 SURYA NARAYAN THAKUR, Department of Physics, Banaras Hindu University, Varanasi, Uttar Pradesh, at high laser intensities. We evaluated the SPM effects by measuring the India. optical spectra of the ultrashort pulses as well as the fs-CARS spectrum 0.5 transmitted through our custom-designed high-pressure vessel. Different Gallstone formation in the gallbladder is common in India. Molecular composition of the gallstone is not well known O2 CO2 till date. But the knowledge of the molecular composition of different kinds of gallstones can provide a significant clue for SPM patterns and the extent of SPM were evaluated for gaseous species Intensity (a.u.) 0.0 like N2,CO2 and CH4. With the suppression of SPM by reducing the 12500 13000 12500 13000 its formation and treatment. Thus in the present paper molecular composition of gallbladder stone has been investigated laser intensity, fs-CARS spectrum in pure N2 was successfully fitted for Wavennumber(cm−1) Wavennumber(cm−1) by means of photoacoustic spectroscopy (PAS) as it does not require any sample preparation. The PA spectra of gallstone pressure range from 1 to 10 bar. This study is meaningful not only for the samples are recorded using PA spectrometer developed in our laboratory. The presence of cholesterol, calcium carbonate, and study of fs-CARS measurement but also for all the other ultrafast spec- bilirubine, in the photoacoustic spectrum, have been recognized and compared with its UV-Visible absorption spectrum. The troscopic studies at high pressure conditions, especially when the laser beams need to be focused or if the optical path inside results of this investigation show that PAS is more suitable to detect the presence of the different molecular composition in the high pressure chamber is significant. gallstones as compared to conventional absorption spectroscopy. 212 213

RL08 Post-Deadline Abstract 4:27 – 4:42 RL10 5:03 – 5:18 OBSERVATION OF SOME Ω=1/2 ELECTRONIC STATES OF NICKEL DEUTERIDE, NiD, WITH LASER-INDUCED ELECTROCHEMICAL SURFACE-ENHANCED RAMAN SPECTRA AND PLASMON-DRIVEN PHOTOELECTRO- FLUORESCENCE CHEMICAL REACTION OF P-AMINOTHIOPHENOL ON SILVER ELECTRODE OF NANOSTRUCTURES

AMANDA J. ROSS, PATRICK CROZET, UMR 5306, ILM University Lyon 1 and CNRS, Villeurbanne, MENG ZHANG, DE-YIN WUa, ZHONG-QUN TIAN, College of Chemistry and Chemical Engineering, Xia- France; ALLAN G. ADAM, Department of Chemistry, University of New Brunswick, Fredericton, NB, Canada; men University, Xiamen, China. DENNIS W. TOKARYK, Department of Physics, University of New Brunswick, Fredericton, NB, Canada. Surface plasmon resonance (SPR) of noble metal nanoparticles (NPs) provides a pathway to efficiently absorb and confine The five lowest-lying electronic states of nickel hydride (NiH) are usually labeled light to nanoscale surface electrons, thereby bridging photonics and photoelectrochemistry. This not only produces the giant 2Δ 2Π 2Δ 2Σ+ 2Π Raman intensity enhancement in surface-enhanced Raman spectroscopy (SERS), but also results in plasmon-driven chemical 5/2, 3/2, 3/2, 1/2 and 1/2, although there is significant mixing between them. These states arise from the d9 electron configuration of Ni+, perturbed by an H− ligand. A reaction on metal nanostructures. We have studied the surface-enhanced Raman spectra of p-aminothiophenol adsorbed variety of vibrational levels has been observed in each, and the aggregate data set has been on silver electrodes of nanostructures. In this work, we studied SPR-enhanced photoelectrochemical synergistic reactions by well modelled as a ‘supermultiplet’ by the Field groupa. SERS to improve chemical reaction activity and examine changes in reaction selectivity. We first demonstrate that hot carriers 2Δ 2Π 2Δ arising from SPR decay contribute to the surface catalytic coupling reaction of PATP on a silver NP electrode. Then, by using For the deuterated isotopologue NiD, only the 5/2, 3/2 and 3/2 states have potential step electrochemical SERS, we further inspect the kinetics of the surface catalytic coupling reaction by monitoring been reported in the literature. A multi-isotope supermutiplet fitting including both the −1 NiH and (more limited) NiD datab provided predictions for the two Ω=1/2 states of the the time-dependent SERS intensity of the characteristic band at 1436 cm , which can be attributed to the stretching vibration NiD supermultiplet. Experimental observation was needed to validate (and improve) the of the N=N double bond of p,p’-dimercaptoazobenzene (DMAB). When synergistically combined with the modulation of model. pH at electrochemical interfaces, SPR-enhanced photoelectrochemical reactions can be further gain reaction efficiency and We report on laser-induced fluorescence experiments conducted both at the University of New Brunswick and at Uni- selectivity for the formation of DMAB and other surface species at higher potentials. The electrochemical SPR effect provides 2Σ+ =01 2 2Π =01 a viable approach for studying the photoelectrochemistry through combining SERS at the interface of nanoparticle-modified versite´ Lyon 1 in which the 1/2,v , , and 1/2,v , levels of NiD were identified and rotationally analyzed. The existing multi-isotope supermultiplet model proved remarkably accurate in predicting the energy and structure of these metal electrodes and electrolytes. Ω=1 2 Ω=1 2 / states. In addition, a higher-lying / electronic state [16.7]0.5 has been identified in NiD, with no obvious aEmail: [email protected] 2Σ+ 2Π analogue in NiH. The [16.7]0.5- 1/2 and [16.7]0.5- 1/2 transitions proved to be a rich source of information about the two lower states.

aJ. A. Gray, M. Li, T. Nelis and R. W. Field, J. Chem. Phys. 95, 7164 (1991) bM. Abbasi, A. Shayesteh, P. Crozet and A. J. Ross, J. Mol. Spectrosc. 349, 49 (2018)

RL09 4:45 – 5:00 3D MOMENTUM IMAGING OF LASER DESORPTION IONIZATION OF 2,5-DIHYDROXYBENZOIC ACID (DHB)

GABRIEL A. STEWART, Chemistry, Wayne State University, Detroit,, MI, USA; DUKE A. DEBRAH, Chem- istry, Wayne State University, Detroit, MI, USA; GIHAN BASNAYAKE, Chemistry, Wayne State University, Detroit,, MI, USA;WENLI,Department of Chemistry, Wayne State University, Detroit, MI, USA.

Matrix-assisted laser desorption ionization (MALDI) is a widely used mass spectrometric technique for the mass analysis of biomolecular compounds. For over three decades since its development a considerable effort has been devoted to increasing the mass resolution and efficiency of MALDI. However, due to a lack of a detailed description of the fundamental processes, underlying the initial ionization, leaves optimization of the method at a trial-and-error endeavor. Generally, MALDI exploits a laser pulse to commence an ionization event where ions, neutrals, and electrons are ejected from the substrate surface into the gas phase (plume). Here we used 3D momentum imaging of laser desorption ionization to investigate the ionization dynamics of dihydroxybenzoic acid (DHB) with different laser pulse durations. Varying the pulse duration between femtoseconds and picoseconds present significantly different dynamics that are reflective of the velocity distributions. These findings suggest that MALDI is not a single molecule process, rather a collective intermolecular phenomenon. 214 215 FA. Astronomy Friday, June 21, 2019 – 8:30 AM FA03 9:06 – 9:21 + Room: 116 Roger Adams Lab H3 IN THE EARLY UNIVERSE Chair: David E. Woon, University of Illinois at Urbana-Champaign, Urbana, IL, USA YU-SHAN M. CHEN, TAKESHI OKA, Department of Astronomy and Astrophysics and Department of Chem- istry, The Enrico Fermi Institute, University of Chicago, Chicago, IL, USA.

+ The chemistry, and radiative and collisional interactions of H3 in the early Universe are examined. The object of study + is to investigate whether H3 is essential in cooling of the primordial gas and thus in the formation of the first stars. The consensus so far is overwhelmingly negative. Most previous papers ignore the possibility at the onset because of the very low FA01 8:30 – 8:45 + −9 concentration of H3 , about 10 of H2 or less. + 2 9 DETECTION OF NON-EMISSION VIBRONIC BANDS OF THIOPHENOXY RADICAL BY ABSORPTION SPEC- Since the dipole infrared emission of H3 is (λ/a) 2 ∼ 10 (λ wavelength: a molecular size) times faster than the + a TROSCOPY quadrupole emission of H2, however, there is a possibility that H3 is comparably efficient coolant as H2. Glover and Savin + was the only paper which took this possibility into account. They negate the contribution of H3 because at a gas density HARUKA SATO, MAYU NEGISHI, Faculty of Science Division I, Tokyo University of Science, Shinjuku-ku, 8 −3 + + + higher than 10 cm H3 number density is further reduced by endothermic reaction H3 +H→ H2 +H2 . We will examine Tokyo, Japan; MITSUNORI ARAKI, Research Institute for Science and Technology, Tokyo University of Science, this. Noda, Japan; TAKAHIRO OYAMA, KOICHI TSUKIYAMA, Faculty of Science Division I, Tokyo University of We will consider the following two effects which have been neglected by the previous workers: (1) the effect of collision Science, Shinjuku-ku, Tokyo, Japan. which convert translational energy of the gas into the energy of vibration and rotation of the molecules and (2) the effect of + spontaneous emission between rotational levels. We find H can be a more efficient coolant than H2 in the early Universe Diffuse Interstellar Bands (DIBs) are absorption bands detected in diffuse clouds by optical observations. Although 3 depending on temperature, density, and cosmological conditions of the primordial gas at the time of star formation. ∼ 600 DIBs have been found so far, only the five bands were assigned to the fullerene cation and the other bands are not identified yet. Recently, benzonitrile (C6H5CN) was detected in interstellar space by radio as the first aromatic compound aGlover, S. C. O. and Savin, D. W. 2009, MNRAS, 393, 911 [1]. Thus, thiophenoxy radical (C6H5S) is received much attentions as a candidate of DIBs, because sulfur is a dominant 2 2 element of interstellar molecules. Fluorescence excitation spectra of the A2–X B1 electronic transition of C6H5S showed the origin band as the strongest peak [2]. However, in our previous work, absorption spectra of phenoxy radical (C6H5O) brought out the stronger vibronic bands than the origin band [3]. The fact suggests that intensities of higher vibronic bands of C6H5S are lost by radiationless transitions in the fluorescence excitation spectra. Thus, stronger vibronic bands of C6H5S are expected because of similarity of the two molecules. We investigated the vibronic bands in the 473–519 nm region by Cavity 2 1 Ring Down spectroscopy and detected them. The strongest vibronic band at 4850 Awas˚ assigned to the 6a0 +6b0 transition. This band may appear as DIB if sufficient amount of this radical exists in interstellar medium. [1] McGuire et al., Science, 359, 202 (2018). [2] Shibuya et al., J. Chem. Phys. 121, 237 (1988). [3] Araki et al., Astronomical J. 150, 113 (2015).

FA04 9:24 – 9:39 ROVIBRATIONAL STUDY OF HNCS PRODUCED VIA ELECTRIC DISCHARGE IN A NEWLY CONSTRUCTED FA02 8:48 – 9:03 MULTIPASS IR CELL AT THE CANADIAN LIGHT SOURCE SYNCHROTRON + H3 ,THEIDEALPROBEFORIN SITU MEASUREMENT OF GALACTIC COSMIC RAYS JENNIFER VAN WIJNGAARDEN, AIMEE BELL, WENHAO SUN, Department of Chemistry, University of Manitoba, Winnipeg, MB, Canada; BRANT E. BILLINGHURST, EFD, Canadian Light Source Inc., Saskatoon, TAKESHI OKA, Department of Astronomy and Astrophysics and Department of Chemistry, The Enrico Fermi Saskatchewan, Canada. Institute, University of Chicago, Chicago, IL, USA.

6 21 A custom-built multipass gas cell capable of supporting a high voltage electric discharge in situ was constructed and Cosmic rays are mysterious particles mostly atomic nuclei with extremely high energy from 10 eV to 10 eV. Their installed on the far infrared beamline at the Canadian Light Source (CLS). The 1.4 m cell can be aligned to achieve a energy spectra for many nuclei are known in detail from the measurements on the earth. To measure cosmic rays in the −1) + total absorption pathlength of 24 m and when combined with a Bruker IFS12HR FTIR spectrometer (0.000959 cm and Galaxy, however, we need a chemical method using spectroscopy. H provides the ideal probe for this purpose because of 3 synchrotron light, this new experiment is designed to collect high resolution infrared spectra of the complex mixture of (1) its ubiquity, (2) simple chemistry, and (3) concise spectrum. + molecular species generated in a high voltage (up to 3 kV) discharge. Preliminary tests have included CH3NCS as a precursor For about 30 years from the classic paper by Spitzer and Tomaskoa,whenH was used as the probe, the cosmic ray −17 −1 to generate HNCS, a known astronomical species. The rich spectra recorded at the CLS include series of pure rotational ionization rate of H2 was thought to be on the order of ζ ∼ 10 s and uniform throughout the Galaxy. The 1997 −1 + transitions in the far IR region below 500 cm and rotationally resolved vibrational bands of which the strongest is the CN discovery of H in diffuse clouds and in the Galactic center (GC), however, changed this picture drastically. It is now 3 stretching mode at 1989 cm−1. The ongoing analysis of the rovibrational spectrum of this highly fluxional molecule will established that ζ in diffuse clouds is 10 times higher than in dense cloudsb and ζ in the Central Molecular Zone of the GC be discussed. These preliminary studies lay the foundation for improved descriptions of the lowest energy states of floppy is 1000 times higherc. The uniformity of cosmic ray energy density throughout the Galaxy which was once thought to be molecules and the far IR signatures needed to pursue their astronomical detection. reasonable because of its high penetrability has been negated. I will analyze these results using the Bethe formula for the cross section of ionization and discuss their implication in astrophysics and astrochemistry.

aSpitzer, Jr, L. and Tomasko, H. G. 1968, ApJ, 152, 972(1968) bIndriolo, N. and McCall, B. J. 2012, ApJ, 745, 91 cOka, T., Geballe, T. R., Goto, M., Usuda, T., McCall, B. J., and Indriolo, N. 2019, ApJ, submitted Intermission 216 217

FA05 10:18 – 10:33 FA08 11:12 – 11:27 LINE POSITIONS FOR THE ν2 AND ν4 BANDS OF THE 5 ISOTOPOLOGUES OF GERMANE THE 135 – 375 GHZ ROTATIONAL SPECTRUM OF BENZOISONITRILE, AN ISOMER OF THE FIRST INTERSTEL- LAR BENZENE DERIVATIVE DETECTED BY RADIOASTRONOMY CYRIL RICHARD, Laboratoire ICB, CNRS/Universite´ de Bourgogne, DIJON, France; F. KWABIA TCHANA, LISA, CNRS, Universites´ Paris Est Creteil´ et Paris Diderot, Creteil,´ France; JEAN VANDER AUWERA, MARIA ZDANOVSKAIA, BRIAN J. ESSELMAN, R. CLAUDE WOODS, ROBERT J. McMAHON, Depart- ATHENA RIZOPOULOS, Service de Chimie Quantique et Photophysique, Universite´ Libre de Bruxelles, Brus- ment of Chemistry, University of Wisconsin, Madison, WI, USA. sels, Belgium; VINCENT BOUDON, Laboratoire ICB, CNRS/Universite´ de Bourgogne, DIJON, France. Numerous nitrile/isonitrile pairs have been detected in the interstellar medium; the isonitriles are suggested to be gen- Germane (GeH4) is present in the atmospheres of the giant planets erated by nonthermal processes. Benzonitrile (C6H5CN) was recently detected in Taurus Molecular Cloud 1 (TMC-1) by Jupiter and Saturn. Our recent analysis presented the complete modeling radioastronomy. Herein, we report the analysis of benzoisonitrile (C6H5NC, μa = 4.0 D) ground vibrational state and its −1 of line positions and intensities in the ν1/ν3 stretching dyad region near two lowest-energy vibrational states, ν22 (141 cm , calculated at the B3LYP/6-311+G(2d,p) level of theory) and ν33 (155 2100 cm−1a, of great interest for planetary applications. Nevertheless, this cm−1), in the 135 – 375 GHz frequency region. Over 4500 new rotational transitions have been measured in the ground vi- region contains a lot of hot bands. This situation leads to a very dense brational state, main isotopologue. The rotational and distortion constants determined in this work may be used to search for spectrum making deeper analyses difficult. benzoisonitrile in the interstellar medium. The Coriolis-coupled dyad reported herein, containing over 3000 new transitions In this study we present the first analysis and modeling of line posi- for each vibrational state, has been analyzed for the first time, including resonances and several nominal interstate transitions, −1 a tions in the ν2/ν4 bending dyad region for the five isotopologues. This resulting in ΔE22,33 = 9.682258(3) cm and ζ 22,33 = 0.857780(1). Comparisons with the analogous states of benzonitrile analysis was conducted thanks to the formalism and programs developed are discussed. in Dijon and allows to determine energy levels that are well suited for the hot band analyses, and therefore is a great improvement in the develop- ment of an accurate modeling needed for radiative transfer calculation for giant planets. These data will be integrated in our spectroscopic database (GeCaSDab) of calculated positions and intensities as soon as absolute in- tensities will be extracted from the spectra.

aV. Boudon et al., J. Quant. Spectrosc. Radiat. Transfer 205, 174–183 (2018) bhttp://vamdc.icb.cnrs.fr/PHP/gecasda.php

FA06 10:36 – 10:51 H2O ATOMIZATION ENERGY WITH AN aug-cc-pV10Z BASIS SET

NIKESH S. DATTANI, Digital Technologies, National Research Council of Canada, Waterloo, ON, Canada.

The atomization energy of the ground electronic state of H2O is determined with unprecedented precision. The story of how this was obtained, and about future possibilities, is presented.

FA07 10:54 – 11:09 A VARIATIONALLY COMPUTED T =300 K LINE LIST FOR THE METHYL RADICAL CH3

AHMAD Y. ADAM, Faculty of Mathematics and Natural Sciences, University of Wuppertal, Wuppertal, Ger- many; ANDREY YACHMENEV, Center for Free-Electron Laser Science (CFEL), Deutsches Elektronen- Synchrotron (DESY), Hamburg, Germany; SERGEI N. YURCHENKO, Department of Physics and Astronomy, University College London, Gower Street, London WC1E 6BT, United Kingdom; PER JENSEN, Faculty of Math- ematics and Natural Sciences, University of Wuppertal, Wuppertal, Germany.

We present the first variational calculation of a room temperature ab initio line list for the CH3 radical. It is based on a high level ab initio potential energy surface and dipole moment surface of CH3 in the ground electronic state. The ro-vibrational energy levels and Einstein A coefficients were calculated using the general-molecule variational approach implemented in the computer program TROVE. Vibrational energies and vibrational intensities are found to be in very good agreement with the available experimental data. 218 219 FB. Atmospheric science Friday, June 21, 2019 – 8:30 AM FB04 9:24 – 9:39 Room: 100 Noyes Laboratory DEVELOPMENT AND PERFORMANCE OF LILLE’S FOURIER TRANSFORM MILLIMETER-WAVE SPECTROME- Chair: Jacob Stewart, Connecticut College, New London, CT, USA TER

FB01 Post-Deadline Abstract 8:30 – 8:45 LUYAO ZOU,R.A.MOTIYENKO,L.MARGULES,` UMR 8523 CNRS - Universite´ de Lille, Laboratoire PhLAM, Villeneuve d’Ascq, France; E. A. ALEKSEEV, Radiospectrometry Department, Institute of Radio As- CHARACTERIZATION OF HYDROPEROXYMETHYL FORMATE BY MICROWAVE SPECTROSCOPY: MOLECU- tronomy of NASU, Kharkov, Ukraine. LAR INSIGHT INTO AEROSOL FORMATION Fast spectral acquisition is an essential component in obtaining broadband molecular spectra with high signal to noise JESSIE P PORTERFIELD, KELVIN LEE, Radio and Geoastronomy Division, Harvard-Smithsonian Center for ratio, and in studying meta-stable molecular species. With the recent developments on commercially available arbitrary Astrophysics, Cambridge, MA, USA; VALENTINA DELL’ISOLAa, BRANDON CARROLL, MICHAEL C Mc- waveform generators (AWG), direct digital synthesizers (DDS), and room-temperature Schottky diodes, it is feasible now to CARTHY, Atomic and Molecular Physics, Harvard-Smithsonian Center for Astrophysics, Cambridge, MA, USA. perform fast spectroscopy scans using the heterodyne detection of the free induction decay of molecules in the millimeter wave a Hydroperoxide esters are important products in the class of reactions between Criegee intermediates and carboxylic acids. bands, as demonstrated by a few pioneer spectrometer designs. At Lille, we have developed and demonstrated the Fourier b Such reactions are believed to play key roles in the formation of secondary organic aerosols by producing semivolatile and transform millimeter-wave (FTmmW) spectrometer system based on DDS. This spectrometer has a simplified design which low-volatility organic compounds. We provide the first definitive evidence for the most fundamental reaction in this class, that does not require external reference clocks or local oscillators, yet it achieves decent frequency resolution and high phase between carbonyl oxide CH2OO and formic acid HCOOH to form hydroperoxymethyl formate (HPMF), HOOCH2OCHO. stability. Since then, several upgrades, including new frequency sweep scheme and filter applications, have been made to Using a modified continuous flow pulsed reactor, HPMF is characterized in the ozonolysis of ethylene by high resolution improve the spectral purity and scan bandwidth of this FTmmW system. The results of the detailed performance test of Fourier transform microwave spectroscopy. Evidence for the most stable conformer - a seven membered, hydrogen bond bandwidth, sensitivity and data acquisition rate on the upgraded system will be presented. The advantages and limitations of stabilized ring - is supported with high level calculations and observation of 13C isotopologues in natural abundance. the spectrometer for conducting fast millimeter spectroscopy on atmospheric radicals will be discussed. The authors thank the Region´ Hauts-de-France, and the Ministere` de l’Enseignement Superieur´ et de la Recherche (CPER aCo-affiliation University of Bologna Climibio), the French ANR Labex CaPPA through the PIA (contract ANR-11-LABX-0005-01), and the European Fund for Regional Economic Development for their financial support. FB02 8:48 – 9:03 aE. Gerecht, K. O. Douglass and D. F. Plusquellic, 2011, Opt. Expr., 19, 8973; I. A. Finneran, D. B. Holland, P. B. Carrol et al., 2013, Rev. Sci. Instrum., 84, 083104. MEASUREMENT OF VOCs USING OPEN-PATH MID-INFRARED DUAL-COMB SPECTROSCOPY bR. A. Motiyenko and L. Margules,` ISMS 73rd symposium (2018), WI07. KEVIN C COSSEL, GABRIEL YCAS, FABRIZIO GIORGETTA, ESTHER BAUMANN, JACOB T FRIEDLEIN, DANIEL I. HERMAN, ELEANOR WAXMAN, IAN CODDINGTON, NATHAN R. NEWBURY, Applied Physics Division, NIST, Boulder, CO, USA. FB05 9:42 – 9:57 Dual frequency comb spectroscopy (DCS) is a rapidly evolving technique that provides a high-resolution, broadband CONFORMATIONAL LANDSCAPE OF 3-METHOXYPHENOL INVESTIGATED BY JET-COOLED HIGH RESOLU- spectrometer with no instrument lineshape and near perfect frequency calibrationa. These features make DCS well suited TION INFRARED SPECTROSCOPY for accurate measurements of multiple species simultaneously. Because the frequency comb lasers can be well collimated, such a system can be used for long open-path measurements with path lengths ranging from hundreds of meters to several PIERRE ASSELIN, YACINE BELKHODJA, YANN BERGER, CNRS, De la Molecule´ aux Nano-Objets: kilometers. Open-path measurements of atmospheric gas species over these path lengths are well suited to quantify emissions Reactivit´ e,´ Interactions, Spectroscopies, MONARIS, Sorbonne Universite´ , PARIS, France; JONAS BRUCK- from sources like oil and gas, forest fires, and industry. HUISEN, Institute for Physical Chemistry, RWTH Aachen University, Aachen, Germany;ARNAUDCUISSET, Previous demonstrations of open-path DCS have primarily been in the 1-2 μm spectral region; however, in order to reach Laboratoire de Physico-Chimie de l’Atmosphere,` Universite´ du Littoral Coteˆ d’Opale, Dunkerque, France. the sensitivity necessary to detect many atmospheric trace constituents, including volatile organic compounds, operation in the mid-infrared is required. Here, we show a mid-infrared open-path dual comb spectrometer operating in the 3-5 μm spectral Methoxyphenol (MP) are biogenic volatile organic compounds which contribute significantly to biomass burning emis- region. We have used this spectrometer to measure methane, ethane, propane, and butane isomers (arising primarily from oil sions. MP compounds are able to chemically evolve in the atmosphere and several studies aimed to determine the kinetics and gas activity) across a 1-km-long path in Boulder, CO for 1 week with an ethane sensitivity of ∼0.1 ppb for a 2-minute and the reactivity intermediates involved in the tropospheric oxidation processes and the subsequent production of secondary time resolution. In addition, we show quantitative measurements of intentionally released acetone and isopropanol with a 1-σ organic aerosols whose impact to the climate seems to be decisive.[1] The gas phase monitoring of MP in the atmosphere sensitivity of 5.7 ppm · m and 2.4 ppm · m, respectively. requires precise rovibrational cross-sections measurements which can be accurately simulated only if the rotational structures both in the vibrational ground state (GS) and excited states (ES) are understood. Recent rotational studies reported about or- a Coddington I, Newbury N, Swann W. Dual-comb spectroscopy. Optica. 2016 Apr 20;3(4):414. tho (2-MP), meta (3-MP) and para (4-MP) isomers enabled to characterize their conformational landcape from GS rotational and quartic centrifugal constants to reproduce the millimeter-wave spectra at the experimental accuracy.[2,3] Any vibrational FB03 9:06 – 9:21 spectrum of MP compounds resolved in rotation could not be recorded so far, mainly due both to the presence of hot bands A K-BAND MICROWAVE SPECTROMETER FOR STUDYING ATMOSPHERIC REACTIONS and to the complexity of the conformational landscape. Taking advantage of our tunable quantum cascade laser spectrometer coupled to a pulsed slit jet [4] we recorded the infrared spectrum of the ν18 ring in plane bending mode of the 3-MP isomer CHRIS MEDCRAFT, School of Chemistry, UNSW, Sydney, NSW, Australia. around 950 cm−1. Rovibrational analyses supported by the full characterization of the conformational landscape in the GS state [2] provide for the first time unambiguous infrared signatures of two out of four possible conformers of 3-MP including A segmented Chirped Pulse Fourier Transform Microwave (CP-FTMW) spectrometer has recently been installed in a reliable set of ES rotational constants. A more extensive study in the region of CC ring stretching modes is currently in the Molecular Photonics Laboratories at UNSW Sydney. It covers the K-band (18-26 GHz) with an 18 MHz per segment progress to resolve the four conformational signatures of 3-MP and to bring new insights about the conformational flexibility bandwidth. This frequency range permits probing samples at room temperature and in a supersonic expansion. The stable of these compounds. products of atmospheric oxidation reactions of biological and anthropogenic volatile organic carbons (VOCs) will probed in References : [1] A. Lauraguais et al. Atm. Envir. 86, 155-163 (2014).[2] A. Roucou et al. CPC 19, 1-8 (2018). [3] A. a room temperature cell. Reactive and transient species will be probed in a supersonic expansion using a custom discharge Jabri et al., accepted in JCP (2019). [4] P. Asselin et al. PCCP 19, 17224-17232 (2017). mixing nozzle. The nozzle combines a standard high voltage discharge source with a secondary source introduced into the expansion via a capillary gas line. This secondary source is pulsed to reduce gas load and improve sample density. Performance and preliminary results will be presented along with supporting ab initio calculations. Intermission 220 221

FB06 10:36 – 10:51 FB08 11:12 – 11:27 DEMONSTRATION OF A 180 GHZ FULL CMOS SPECTRALLY DISPERSED HETERODYNE RADIOMETER WITH HIGH-RESOLUTION INFRARED SPECTRA AND ANALYSES OF SiF4 InP LNA FOR REMOTE SENSING VINCENT BOUDON, Laboratoire ICB, CNRS/Universite´ de Bourgogne, DIJON, France;LAURENT DEACON J NEMCHICK, BRIAN DROUIN, ADRIAN TANG, YANGHYO KIM, THEODORE J RECK, MANCERON, Synchrotron SOLEIL, CNRS-MONARIS UMR 8233 and Beamline AILES, Saint Aubin, France. MARIA ALONSO, GOUTAM CHATTOPADHYAY, Jet Propulsion Laboratory, California Institute of Tech- nology, Pasadena, CA, USA; YAN ZHANG, M.-C. FRANK CHANG, Electrical Engineering, University of Volcanoes reject large amounts of sulfur-containing gases in the atmosphere;

these represent 10 to 15 % of the anthropogenic sulfur emissions. Thermodynamic  California - Los Angeles, Los Angeles, CA, USA. $% '  considerations show that silicon tetrafluoride (SiF4) should be a normal trace com-  Widespread deployment (both ground-based and spaceborne) of millimeter/submillimeter radiometers for composition ponent of volcanic gases. Some studies report that the possible importance of SiF4

         specific atmospheric retrievals has been hindered by the cost, complexity, and power requirements traditionally associated had been neglected because of the problems of reporting HF and SiF4 separately  $% with this hardware. One possible avenue to make such measurements more routine are millimeter-wave (180-200 GHz) in conventional analyses. However, a better knowledge of spectroscopic parameters  & $%

 heterodyne-detection electronics fabricated with complementary metal-oxide semiconductor (CMOS) process techniques. is needed for this molecule in order to derive accurate concentrations. This is why   $% When outfitted with indium phosphide (InP) low-noise amplifier (LNA) stages, cryogen free system temperatures (Tsys)of we undertook an extensive high-resolution study of its infrared absorption bands, in-  ! ! !  "# 800 - 1000 K can be achieved. This receiver system has been equipped with with a custom 6GS/s ADC / FFT (3GHz band- cluding the fundamentals and several overtone and combinations. We present here    width) system-on-chip to spectrally disperse the generated intermediate frequency signal to allow for composition specific a detailed analysis and modeling of the strongly absorbing ν3 fundamental, for the  a 28 29         measurements of gas-phase samples. The resulting system can be configured to meet the stringent size and power require- there isotopplogues in natural abundance: SiF4 (92.23 %), SiF4 (4.67 %) and    30 ments needed for CubeSat/SmallSat integration thus making for a potentially useful planetary science instrument (i.e., limb SiF4 (3.10 %). Progresses in the analysis of the other bands will be outlined. sounder). This talk will discuss the performance properties of all components, laboratory trails demonstrating sensitivity to rarefied samples of CH3CN and H2O, and future plans for field deployment on ground-based and stratospheric balloon platforms. FB09 11:30 – 11:45 ULTRAVIOLET PHOTOABSORPTION OF SO ISOTOPOLOGUES AND THE B 3Σ− AND C 3Π STATES aY. Kim et al., “A 183-GHz InP/CMOS-Hybrid Heterodyne-Spectrometer for Spaceborne Remote Sensing,” IEEE Trans. THz Sci. Technol.,InReview. ALAN HEAYSa, School of Earth and Space Exploration, Arizona State University, Tempe, AZ, USA;GLENN STARK, Department of Physics, Wellesley College, Wellesley, MA, USA;JAMESRLYONS,School of Earth and Space Exploration, Arizona State University, Tempe, AZ, USA; NELSON DE OLIVEIRA, DESIRS Beamline, Synchrotron SOLEIL, Saint Aubin, France; BRENTON R LEWIS, STEPHEN T GIBSON, Research School of Physics and Engineering, Australian National University, Canberra, ACT, Australia.

The sulphur-monoxide B 3Σ−(v ≥ 4) levels are known to be strongly affected by vibrationally-dependent predissocia- tion and local energy perturbations (Liu et al. 2006 JMS 238:213). The isotope-dependence of this predissociation and the SO photodissociation cross section is a candidate atmospheric-source for explaining the anomalous 32S/33S/34S/36S isotopic FB07 10:54 – 11:09 fractionation found in 2.5Ga old sedimentary material (Ono 2017 Annu. Rev. Earth Pl. Sc. 45:301). SUB-DOPPLER INFRARED SPECTROSCOPY OF JET COOLED CH2Br RADICAL: CH2 STRETCH VIBRATIONS We have recorded new photoabsorption spectra between 195 and 230 nm to determine spectroscopic constants, predis- sociation linewidths, and transition strengths for the excited B 3Σ−(v =4− 17) levels of 32S16O, 33S16O, and 34S16O. The ANDREW KORTYNA, JILA, National Institute of Standards and Technology and Univ. of Colorado, Boulder, 3 3 − 3 − 3 C Π state is also observed and perturbs B Σ (v =4−17) through spin-orbit interaction. B Σ and C Π potential-energy CO, USA; KIRSTIN D DONEY, JILA and NIST, University of Colorado, Boulder, CO, USA; PRESTON G. curves, electronic transition moments, and a global spin-orbit interaction are deduced from the new data so that it may be SCRAPE, DAVID NESBITT, JILA, National Institute of Standards and Technology and Univ. of Colorado, 36 16 extrapolated to the rare S O isotopologue. Boulder, CO, USA. We use the new cross sections to explore the potential for isotope-dependent photodissociation of SO in the ancient-Earth atmosphere due to structured solar UV radiation and atmospheric opacity. The recent use of bromomethyl radical as a novel precursor for producing the simplest Criegee intermediates (CH2OO) motivates our high-resolution investigation of CH2Br.ColdCH2Br (rotational temperature of 20 K) is generated by seeding aNASA Astrobiology Institute, NASA Ames Research Center, Moffett Field, California CH2Br2 into a Ne/He pulsed supersonic slit-jet discharge expansion. Sub-Doppler infrared absorption in the CH2 symmetric stretch band is fully resolved at high single-to-noise ratio, yielding band origins measured at 3052.9781 ± 0.0004 cm−1 for 79 −1 81 CH2 Br and 3052.9775 ± 0.0004 cm for CH2 Br, respectively. The rotationally resolved structure is fitted to a non- rigid rotor Hamiltonian with spin-rotation coupling, furnishing rotational constants and the spin-orbit coupling tensor for the vibrationally excited state. The results are consistent with a vibrationally averaged planar π radical with unpaired electron spin density in a partially filled pπ-orbital on the central carbon atom. These measurements complete the set of high-resolution investigations of the symmetric-stretch mode for mono-halogen substituted methyl radicals (CH3X, X = F, Cl, Br, I). We use this opportunity to examine trends in molecular properties with variation of the substituent halogen atom, for example, regarding vibrationally averaged geometries and symmetric stretch band origins. A combination band is also analyzed, likely originating from the lowest-energy, out-of-plane vibrational bending mode. Evidence of hyperfine structure is observed as well. Interestingly, despite high signal to noise on the symmetric CH stretch vibrational mode, we find no evidence for the asymmetric CH stretch spectrum at our current sensitivities, which we interpret as resulting from strong enhancement of the symmetric stretch band by vibrationally mediated ”charge-sloshing” dynamics in the C-Br bond. 222 223 FC. Clusters/Complexes FC03 9:06 – 9:21 Friday, June 21, 2019 – 8:30 AM IR-INDUCED CHANGE IN THE MICROSCOPIC HYDRATION STRUCTURES OF PHENOL CATIONS TRAPPED IN Room: 1024 Chemistry Annex THE COLD ION TRAP

Chair: Christopher J. Johnson, Stony Brook University, Stony Brook, NY, USA HIKARU SATO, YASUTOSHI KASAHARA, HARUKI ISHIKAWA, Department of Chemistry, School of Sci- ence, Kitasato University, Sagamihara, Japan.

Gas-phase hydrated clusters are treated as a microscopic model of hydration networks. Recently, we have revealed the + a temperature-dependence of hydration structures of hydrated phenol cation, [PhOH(H2O)5] . In the cold condition (30 K), only an isomer having a ring-with-tail type hydration motif (Rt isomer) exists, whereas chain-like isomers (Ch isomer) are dominant in the hot condition (150 K). Isomerizations among the isomers having distinct hydration motifs can be related to structural fluctuations in the bulk systems. Thus, we have investigated the isomerization of the hydrated phenol cation trapped in the cold trap. In the last symposium, we reported the observation of the isomerization from the Rt to the Ch isomers. FC01 8:30 – 8:45 However, the quality of the spectra was not good enough. To improve the signal to noize ratio of the spectra, we introduced HYDROGEN BOND NETWORKS IN THE SOLVATION OF THE SIMPLEST SUGAR an octopole ion trap instead of the 22-pole ion trap, since an spatial overlap between the ions and the laser beam is expected to be better. In the present paper, we will report the progress of our study involving the time profile of the isomerization induced CRISTOBAL PEREZ, AMANDA STEBER, MELANIE SCHNELL, FS-SMP, Deutsches Elektronen- by the IR excitation. Synchrotron (DESY), Hamburg, Germany. aH. Ishikawa, I. Kurusu, R. Yagi, R. Kato, Y. Kasahara, J. Phys. Chem. Lett. 8, 2641 (2017). The vast majority of biological processes takes place in aqueous environments. The biomolecule’s biological function is therefore strongly influenced by its interactions with the solvating water molecules. Quantifying these interactions at a molecular level, when the organic molecule of interest is only surrounded by a few water molecules, serves as a valuable route to better understand the particular molecular behavior. In this talk, we will present our results on the stepwise hydration of Glycoaldehyde (Gly) from broadband rotational spectroscopy. Taking advantage of the high resolution and sensitivity of this technique, the experimental structures of (Gly)-(H2O)n (n=1-5) clusters have been determined and will be presented. 18 An unambiguous identification of these clusters has been achieved from the spectra of the parent species and H2 O single substitution of the water units within the clusters. These experiments allowed for an accurate determination of the oxygen- atom framework in the cluster. The experimental hydrogen bond networks will be discussed and compared to those of bare water clusters showing that certain topologies are recurrent.

FC04 9:24 – 9:39 FRANCK-CONDON-LIKE PATTERNS OBSERVED IN THE INFRARED SPECTRA OF PHENOL-ALKYLSILANE DIHYDROGEN-BONDED CLUSTERS IN THE EXCITED STATES

MASAAKI UCHIDA, TAKUTOSHI SHIMIZU, YASUTOSHI KASAHARA, Department of Chemistry, School FC02 8:48 – 9:03 of Science, Kitasato University, Sagamihara, Japan; YOSHITERU MATSUMOTO, Department of Chemistry, IR SPECTROSCOPY OF GLYCINE-WATER CLUSTERS IN HELIUM NANODROPLETS Faculty of Science, Shizuoka University, Shizuoka, Japan;HARUKIISHIKAWA, Department of Chemistry, School of Science, Kitasato University, Sagamihara, Japan. NITISH PAL, DEVENDRA MANI, RAFFAEL SCHWAN, TARUN KUMAR ROY, GERHARD SCHWAAB, We have been carrying out spectroscopic studies on the Si-H···H-O type dihydrogen-bonded clusters. It was revealed Physikalische Chemie II, Ruhr University Bochum, Bochum, Germany; BRITTA REDLICH, LEX VAN DER ··· MEER, Institute for Molecules and Materials (IMM), Radboud University Nijmegen, Nijmegen, Netherlands; that the strength of the Si-H H-O type dihydrogen bond is comparable to that of the dispersion interaction and that the MARTINA HAVENITH, Physikalische Chemie II, Ruhr University Bochum, Bochum, Germany. cluster structure is determined by the balance between these two interactions. To examine an effect of a change in the balance between them, we recorded the IR spectra of phenol-alkylsilane clusters in the S1 state. In the course of our study, we found We have studied water induced zwitterionization of glycine using helium nanodroplets isolation infrared spectroscopy. that the OH stretching band profile consists of several bands involving the excitation of the intermolecular vibrational modes. In the past, this process has been studied using matrix isolation infrared spectroscopy.1 However, spectroscopic fingerprint These band profiles are referred to as the Franck-Condon-like patterns. In the case of the phenol-t-butyldimethylsilane cluster, for zwitterion formation could not be assigned, unambiguously. This triggered various theoretical studies for predicting the the band patterns simulated based on the Franck-Condon factors for the intermolecular vibrational mode have reproduced the 2 observed patterns very well. This behavior indicates the interaction between the OH stretch and intermolecular vibrational energetic stabilization and vibrational fingerprint of zwitterionic glycine-(H2O)n (n=1-10) clusters. In this study, we have exploited the barrier free diffusion property of helium droplets to stepwise add water molecules to one molecule of glycine. modes. On the other hand, the infrared spectra of the electronic excited states of phenol-ethyldimethylsilane dihydrogen- −1 bonded cluster indicate the contribution of two intermolecular vibrational modes. In this case, we analyzed the band pattern Herein we present the infrared spectra of glycine-(H2O)n clusters recorded in the range of 1000-1850 cm ,usingthefree electron lasers (FELs) at FELIX laboratory in Nijmegen. involving effects of the Duschinsky rotation as well as the displacements of the equilibrium positions for the vOH =0and1 References: 1) R. Ramaekers, J. Pajak, B. Lambie and G. Maes, J. Chem. Phys., 120, 4182 (2004). 2) R. Perez de Tudela states. In the present paper, we report the details of the analysis of the Franck-Condon-like patterns. and D. Marx, J. Phys. Chem. Lett., 7, 5137 (2016). Note: This work was supported by the Cluster of Excellence RESOLV (Ruhr-Universitat EXC1069) funded by the Deutsche Forschungsgemeinschaft, Stichting voor Fundamenteel Onderzoek der Materie (FOM) and LASERLAB-EUROPE grant 654148 for the support of the FELIX Laboratory.

Intermission 224 225

FC05 10:18 – 10:33 FC08 11:12 – 11:27 PLANAR ION FUNNEL FOR IMPROVED CONTROL OF ION TRANSMISSION AND TEMPERATURE IN CLUSTER MEASURING THE ELECTRONIC ABSORPTION SPECTRA OF GOLD NANOCLUSTERS VIA MASS SELECTIVE STUDIES UV-VIS SPECTROSCOPY

CARLEY N FOLLUO, ABBEY McMAHON, JARRETT MASON, CAROLINE CHICK JARROLD, Depart- HANNA MORALES HERNANDEZ, ANTHONY CIRRI, CHRISTINA KMIOTEK, CHRISTOPHER J. JOHN- ment of Chemistry, Indiana University, Bloomington, IN, USA. SON, Chemistry, Stony Brook University, Stony Brook, NY, USA.

Cluster anions are commonly made in Smalley-type laser ablation sources, which generate a wide range of species in Nanoscale engineering shows tremendous promise for developing new devices in energy transfer and storage, chemical different charge states, potentially causing ion loss due to charge recombination in thermalization channels. We present an synthesis, sensing, and a host of other applications. These applications critically depend on controlling electronic structure, anion photoelectron spectroscopy study of anions selectively funneled into a thermalization channel using a planar ion funnel but synthetic and experimental limitations hamper efforts to link electronic structure to dynamics and chemistry. We are over- (PIF). This funnel can increase ion current and allow selection of different portions of the ion plume generated in the cluster coming these limitations by recording gas-phase, ultraviolet-visible (UV-Vis) spectra of ligand-protected gold nanoclusters source. The vibrational temperatures of funneled anions are evaluated by analysis of hot band transitions, and we present the with compositions precisely selected from a mixture by mass spectrometry. Clusters consisting of 6 to 9 gold atoms and vary- advantages and disadvantages of implementing this mass spectrometric tool in studies that rely on ablation for ion production. ing ligand count and type were collected at 36 K and 4 K, with nitrogen and helium gas, respectively, physisorbing onto the surface of the clusters and acting as solvents. These spectra provide an unprecedented level of detail on the electronic structure of the clusters due to the homogeneous, contaminant-free environment and cryogenic temperatures in our instrument. With the aid of computational studies, experiments and analysis are underway to definitively assign the spectral features and to determine the factors that lead to shifts and splitting of transitions. The number and type of ligand and solvent species have a significant impact on transitions expected to involve only core metal atoms. Tracking the changes in the electronic transitions FC06 10:36 – 10:51 of gold nanoclusters with respect to chemical composition and structure will allow us to develop design rules to chemically DIMERIZATION EFFECT ON HF ELIMINATION FROM THE PHOTOIONIZED FLUOROPHENOLS manipulate their electronic structure, analogous to those developed for organic and organometallic molecular systems.

PIYALI CHATTERJEE, SOUVICK BISWAS, TAPAS CHAKRABORTY, Physical Chemistry, Indian Associa- tion for the Cultivation of Science, Kolkata, India.

A time of flight mass spectrometry study for multi-photon ionization dissociation of monomers and dimers of 2- and 3-fluorophenols (2FP and 3FP) by a pulsed UV laser light of wavelength 266 nm will be presented. For these molecules, HF elimination from the excited and ionic states is a vital reaction channel. Our measurements reveal that the reaction does not occur from the monomer of 3FP, but it does occur with a measurable yield from the monomer cation of 2FP. On the other hand, upon formation of hydrogen bonded dimers, this reaction is triggered in the cation of 3FP, but for 2FP dimer cation the reaction is so facile that no intact dimer cation survives and only the HF eliminated dimer ion shows up in the mass spectrum. Electronic structure theory predicts that in the D0 state of 2FP dimer cation, HF elimination is exothermic, but the process encounters a large barrier, 2.75 eV. However, in S1 state of the dimer the reaction is predicted to be barrierless. Thus, we propose that for this dimer, HF elimination takes place in the intermediate S1 state, and the remaining fragment that has relatively lower ionization energy is ionized effectively by an overall two-photon (1+1) process. For the reaction to occur from 3FP dimer cation, a rearrangement of the dimer geometry and formation of an intermediate adduct has been suggested, and it is argued that the latter could be produced by nucleophilic attack of the neutral moiety at the ortho site of the cationic counterpart, and the whole process requires 3-photon (2+1) absorption.

FC07 10:54 – 11:09 + INFRARED SPECTROSCOPY OF [(H2S)2(X)1] (X = WATER, METHANOL, AND ETHANOL): INFLUENCE OF THE MICROSOLVATION ON THE HEMIBOND

KEIGO HATTORI, DANDAN WANG, ASUKA FUJII, Department of Chemistry, Tohoku University, Sendai, Japan.

Changes of the excess charge accommodation motif in hemibonded hydrogen sulfide by microsolvation are studied by + + infrared spectroscopy of the [(H2S)2(X)1] (X = water, methanol, and ethanol) clusters. While the hemibond in the (H2S)2 ion core is stable to the microhydration by a single water molecule, it is broken by the proton transfer with the microsolvation by a single methanol or ethanol molecule. Hetero hemibond formation between hydrogen sulfide and these solvent molecules + + + is not observed. On the other hand, the H3S ion core in the protonated H (H2S)2 cluster is switched to H3O ion core by the microhydration with a single water molecule, even though the proton affinity of water is lower than that of hydrogen sulfide. 226 227 FD. Radicals Friday, June 21, 2019 – 8:30 AM FD03 9:06 – 9:21 Room: 217 Noyes Laboratory LASER-INDUCED FLUORESCENCE STUDY OF JET-COOLED TUNGSTEN MONOXIDE (WO) IN GAS PHASE Chair: Laura R. McCunn, Marshall University, Huntington, WV, USA JIE YANG, JICAI ZHANG, XINWEN MA, Atomic and molecular physics, Institute of Modern Physics, Lanzhou, CHINA.

FD01 8:30 – 8:45 Combining laser ablation and pulsed discharge supersonic beam tech-   INFRARED SPECTRA OF THE 2,3-DIHYDROPYRROL-2-YL AND 2,3-DIHYDROPYRROL-3-YL RADICALS ISO- niques, we investigated the laser-induced fluorescence (LIF) excitation spec- tra of jet-cooled WO molecule in the range of 18900 – 23500 −1.Fig.1 LATED IN SOLID PARA-HYDROGEN cm  (a) shows our experimental setup, where the gas phase WO molecules were JAY C. AMICANGELO, School of Science (Chemistry), Penn State Erie, Erie, PA, USA; YUAN-PERN LEE, produced by the reaction of O2 molecules with the tungsten atoms ablated Applied Chemistry, National Chiao Tung University, Hsinchu, Taiwan, Institute of Atomic and Molecular Sci- from a pure tungsten target. In this energy range, totally 63 bands were ob- ences, Academia Sinica, Taipei, Taiwan. served, and 60 bands were classified to 10 electronic transition progressions as shown in Fig.1 (b). Among them, 6 electronic transition progressions were The reaction of hydrogen atoms (H) with pyrrole (C4H5N) in solid para-hydrogen (p-H2) matrices at 3.2 K has been previously reported by Ram et al. [1] using Fourier transform emission (FTE) + + + + + + + studied using infrared spectroscopy. The production of H atoms for reaction with C4H5N was essentially a three step process. spectroscopy, 4 electronic transition progressions [21.2]0 –X0 ,[21.5]0 –X0 , [22.2]0 –X0 , and [23.3]1 – X0 were First, mixtures of C4H5N and Cl2 were co-deposited in p-H2 at 3.2 K for several hours, then the matrix was irradiated with only identified in the LIF spectra. The symmetry of all upper electronic states were determined using the ducted selection ultraviolet light at 365 nm to produce Cl atoms from the Cl2, and finally the matrix was irradiated with infrared light to induce rules in the known symmetry of the ground state. Among the four transition systems only observed in LIF spectra, three elec- + + + + + + the reaction of the Cl atoms with p-H2 to produce HCl and H atoms. Upon infrared irradiation, a series of new lines appeared tronic states have the 0 symmetry, which are [21.2]0 , [21.5]0 , and [22.2]0 states. Considering the E0 and F0 states, + in the infrared spectrum, resulting from the products of the H + C4H5N reaction. To determine the grouping of lines to there are five electronic states having the symmetry of 0 in this energy region. Ram et al. performed a high-level ab initio distinct chemical species, secondary photolysis was performed using 533-nm and 455-nm light-emitting diodes. Based on the calculation of the lowest three configurations of WO molecule involving to the electron promotions of 3σ→1δ,1δ→2π, and + secondary photolysis, it was determined that the majority of the new lines belong to two distinct chemical species, designated 3σ→2π, respectively, in which only two states have the 0 symmetry in this energy region. Therefore, it is a great challenge as set A (3491.0, 2754.4, 1412.7, 1260.4, 1042.8, 963.2, 922.1, 673.6 cm−1) and set B (3468.3, 2784.9, 1470.6, 1449.5, for the theoretical calculation to comprehensively understand the electronic structure of WO molecule. 136.3, 1266.5, 1151.1, 1098.0, 960.6, 949.5, 924.0, 860.8, 574.2 cm−1). The most likely reactions to occur under the low References: [1] R. S. Ram, J. Lievin´ b, Peter F. Bernath, J. Mol. Spectrosc. 256, 216 –227 (2009). temperature conditions in solid p-H2 are the addition of the H atom to the nitrogen atom or the two carbon atoms of C4H5N to produce the corresponding hydrogen atom addition radicals (H-C4H5N). Quantum-chemical calculations were performed at the B3PW91/6-311++G(2d,2p) level for the three possible H-C4H5N radicals in order to determine the relative energetics and the predicted vibrational spectra for each radical. The addition of the H atom to carbons 2 and 3 is predicted to be exothermic by 112.1 and 76.1 kJ/mol, respectively, while the addition of the H atom to the nitrogen is predicted to be endothermic by 67.8 kJ/mol. When the lines in set A and B are compared to the scaled harmonic and anharmonic vibrational spectra for all three possible radicals, the best agreement for set A is with the radical produced by the addition to carbon 3 (2,3-dihydropyrrol-2-yl FD04 9:24 – 9:39 radical) and the best agreement for set B is with the radical produced by addition to carbon 2 (2,3-dihydropyrrol-3-yl radical). VISIBLE VIBRONIC EMISSION SPECTROSCOPY OF JET-COOLED BENZYL-TYPE RADICALS GENERATED FROM 4-CHLORO-M-XYLENE

FD02 8:48 – 9:03 SANG LEE, Department of Chemistry, Pusan National University, Busan 46241, Republic of Korea. MATRIX-ISOLATION FTIR SPECTROSCOPY OF THE DEHYDRO-PYRAZINE RADICAL Transient species such as molecular ions and radicals are believed to play an important role as reaction intermediates MAYANK SARASWAT, SUGUMAR VENKATARAMANI, Department of Chemical Sciences, Indian Institute in chemical reactions. Thus, the spectroscopic studies of molecular radicals could provide a proper understanding to the of Science Education & Research, Mohali, Punjab, India. characteristics of the chemical reactivity in reaction dynamics. Ring-substituted benzyl-type radicals always exhibit the D1 → D0 electronic transition energies being shifted to red region with respect to the parental benzyl radical. The red-shift of Photochemistry of nitrogen-based heterocyclic radicals plays a vital role in our understanding of the fundamental chem- the electronic transition strongly depends on the numbers, types, and positions of substituents.a In this work, two types of a ical processes in multiple fields including combustion, and atmospheric/troposphere chemistry . Photochemical studies pro- benzyl-type radicals, 2-chloro-5-methylbenzyl and 4-chloro-3-methylbenzyl radicals were generated in corona discharge by vide insights about the mechanistic pathways and the origin of various interstellar molecules. Radical and biradical species a simple dissociation of methyl C-H bond at the different position of 4-chloro-m-xylene using a pinhole-type glass nozzle containing heteroatoms play a significant role as intermediates in photochemical processes. The photolysis and pyrolysis in a technique of corona excited supersonic expansion which has been well developed in this laboratory over the past 20 b studies of one such heterocycle, pyrazine have been done using various spectroscopic and computational techniques .How- years. The observed vibronic bands at 20342 and 21564 cm−1were, respectively, assigned to the origin bands of the 2-chloro- ever, the photochemical investigations of the pyrazine radical have not been reported so far. In this work, we have explored 5-methylbenzyl and 4-chloro-3-methylbenzyl radicals, red-shifted by 1660 and 438 cm−1from the benzyl radical at 22002 the electronic structures of the radicals corresponding to all the possible diazines- pyrimidine, pyridazine, and pyrazine, at cm−1. In this presentation, the identification of radical species and assignments of vibronic bands will be described. In various levels of theories. Investigations for 3c-5e interactions between the two nitrogen lone pairs and the radical center have addition, the variation of red-shifts with substitution position will be discussed in terms of rotational motion of delocalized π c also been carried out . This has been coupled with an experimental study; the photochemical generation and characterization electrons over the molecular plane. The existence of nodal points greatly reduces the space available for rotational motion of of the pyrazine radical using Matrix Isolation FT-Infrared spectroscopy. Isolated pyrazine radical photochemistry in solid delocalized π electrons by breaking off the hyperconjugation between benzene ring and substituent. b nitrogen and argon matrices at 4 K using strong UV irradiation leads to the formation of numerous products via ring open- a ing and fragmentation channels, which were identified by comparing the experimental spectrum with the computationally C. Branciard-Larcher, E. Migirdicyan, and J. Baudet Chem. Phys. 2, 95-106 (1973). bM. Lim and S. K. Lee, Chem. Phys. Lett. 713, 10-14 (2018). obtained spectrum.

aPeeters, Z. et al., A&A 2005, 433, 583-590. bWilhelm, M. J. et al., J. Phys. Chem. A 2018, 122, 9001-9013. cSaraswat, M. et al., Phys. Chem. Chem. Phys. 2018, 20, 4386-4395. Intermission 228 229

FD05 10:18 – 10:33 FD07 10:54 – 11:09 IONIZATION ENERGIES AND SINGLE VIBRONIC LEVEL EMISSION (SVLE) SPECTROSCOPY OF CIS- AND ELECTRONIC STRUCTURE OF OH·ISOPRENE ADDUCTS FROM ANION PHOTOELECTRON IMAGING SPEC- TRANS-1-VINYLPROPARGYL RADICALS TROSCOPY

JONATHAN FLORES, MEREDITH WARD, SEDERRA D. ROSS, NEIL J REILLY, Chemistry, University of MARISSA A. DOBULIS, MICHAEL C THOMPSON, KELLYN M. PATROS, CAROLINE CHICK JARROLD, Massachusetts Boston, Boston, MA, USA. Department of Chemistry, Indiana University, Bloomington, IN, USA.

The resonance-stabilized 1-vinylpropargyl radical (1vpr), which can adopt cis- and trans- conformations, is held to be a Isoprene is the most prevalent non-methane volatile organic compound in the atmosphere, comprising about half of non- a significant intermediate in hydrocarbon pyrolysis and has also been observed in the crossed-beam reaction of C2 with propyne. methane total biogenic emissions. Oxidation of isoprene by hydroxyl radicals results in important and diverse atmospheric We have cleanly generated 1vpr in a discharge of pent-1-ene-4-yne and measured the adiabatic ionization energy (AIE) of chemistry, including the formation of secondary organic aerosols and other atmospheric radicals.b However, the high reac- each conformer by two-colour ion-yield spectroscopy. Our work takes advantage of an earlier report by one of us of the tivity of the hydroxyl-isoprene (OH-isoprene) complex with oxygen and water makes direct measurements difficult in situ. 1vpr electronic origin bands near 460 nm and 470 nm. Extrapolation to zero-field yields AIEs of 7.823(1) eV and 7.894(1) eV We utilize anion photoelectron spectroscopy as a “back-door” technique to examine vibrational and electronic structure of for the trans- and cis- forms respectively, in superb agreement with a QCISD(T) calculation (Hansen et al.,J.Phys.Chem. the OH-isoprene adduct. Spectral assignment is aided by quantum chemical calculations. Structural variations between anion A 2006, 110, 4376-4388), and further supporting the identification of 1vpr in flames. As part of on-going work, we have and neutral species result in significant vibrational progressions. These progressions appear to resemble low electron bind- also secured vibrational assignments for a number of levels in the ground and first excited states of both conformers, first ing energy features in the photoelectron spectrum, but additional higher electron binding energy features attributed to other by decomposing the mass-resolved electronic spectrum (as much as possible) into cis- and trans- contributions using hole- species are also present. Potential explanations of these features will be explored. burning spectroscopy, and then by measuring SVLE spectra for sufficiently well-resolved bands. The apparent projection of a aGuenther, A. et al. J. Geophys. Res. 100, 8873–8892 (1995) low-frequency excited state mode onto both a and a levels in the ground state is taken as evidence of a Duschinsky rotation bWennberg, P. O., et al. Chem. Rev. 118, 3337-3390 (2018) that mixes a and a modes, and perhaps, therefore, of some reduction in planarity in the excited state, particularly for the cis isomer. The extent to which this interpretation is reflected by B3LYP and CASSCF calculations will be discussed. FD08 11:12 – 11:27 ANION PHOTOELECTRON IMAGING SPECTROSCOPY OF REACTION INTERMEDIATES IN THE OZONOLYSIS OF ISOPRENE

MARISSA A. DOBULIS, MICHAEL C THOMPSON, CAROLINE CHICK JARROLD, Department of Chem- istry, Indiana University, Bloomington, IN, USA.

Ozonolysis of volatile organic compounds is one of the principle oxidative reactions in the atmosphere. Such reactions are known to produce hydroxyl radical, as well as secondary organic aerosols.a Isoprene is the most abundant non-methane hydrocarbon in the troposphere, and is thought to be a nighttime source of hydroxyl radical in densely vegetated areas.b We “tag” unstable radical species with an electron in order to study their molecular identities and low-lying electronic structures FD06 10:36 – 10:51 via mass spectrometry and anion photoelectron spectroscopy. We will present photoelectron spectra of products of isoprene ozonolysis at 2.33 and 3.49 eV, along with quantum chemical calculations of several reaction intermediates that are formed IDENTIFYING AN UNKNOWN ISOMER OF C7H7 OBSERVED IN JET-COOLED HYDROCARBON DISCHARGES via ozonolysis of isoprene.

MEREDITH WARD, JONATHAN FLORES, SEDERRA D. ROSS, Chemistry, University of Massachusetts aGuenther, A. et al. J. Geophys. Res. 1995, 100, 8873–8892. Boston, Boston, MA, USA; LAURA M McCASLIN, Fritz Haber Center for Molecular Dynamics and Institute bGutbrod, R. et al. J. Am. Chem. Soc. 1997, 119, 7330-7342. of Chemistry, The Hebrew University of Jerusalem, Jerusalem, Israel; JOHN F. STANTON, Quantum Theory Project, University of Florida, Gainesville, FL, USA;NEILJREILLY, Chemistry, University of Massachusetts Boston, Boston, MA, USA.

We describe on-going efforts to diagnose the hydrocarbon carrier of an electronic band system observed near 459 nm. The spectral carrier can be produced in jet-cooled discharges of toluene and linear and cyclic heptatrienes, but is most effi- ciently generated from 1,6-heptadiyne. The spectrum is observed at m/z =91by resonant two-colour ionization, has an origin at the same wavelength in Ne and Ar expansions, and almost certainly does not result from photofragmentation of heav- ier species. Several ground-state frequencies have been obtained from single-vibronic-level emission (SVLE) spectroscopy. Optical-optical hole-burning and two-colour ion-yield measurements reveal that the spectrum arises from a single isomer with an adiabatic ionization energy near 6.93 eV. On this basis, a large number of C7H7 radicals can be simply ruled out using relatively inexpensive electronic structure calculations. The resonance-stabilized, substituted allylic radicals 1,2,5,6- heptatetraen-4-yl and 2-ethynylcyclopentenyl have predicted (CBS-QB3) AIEs within ∼ 0.1 eV of experiment, but simula- tions of Franck-Condon activity in totally symmetric modes from CCSD and EOM-CCSD calculations disagree qualitatively with the experimental origin SVLE spectrum, for both isomers. The 1-ethynylcyclopentenyl radical, which can be viewed as hosting an embedded, strained 1-vinylpropargyl radical chromophore (absorbing near 462 nm), is under investigation at the time of writing. 230 231 FE. Lineshapes, collisional effects FE03 9:06 – 9:21 Friday, June 21, 2019 – 8:30 AM PHOTOACOUSTIC SPECTROSCOPY OF THE O2 A-BAND IN SUPPORT OF REMOTE SENSING ELIZABETH M LUNNY, Division of Chemistry and Chemical Engineering, California Institute of Technol- Room: B102 Chemical and Life Sciences ogy, Pasadena, CA, USA; MATTHEW J. CICH, Jet Propulsion Laboratory, California Institute of Technology, Pasadena, CA, USA; THINH QUOC BUI, JILA, National Institute of Standards and Technology and Univ. of Col- Chair: Shanshan Yu, California Institute of Technology, Pasadena, CA, USA orado Department of Physics, University of Colorado, Boulder, Boulder, CO, USA; DAVID A. LONG, JOSEPH T. HODGES, Material Measurement Laboratory, National Institute of Standards and Technology, Gaithersburg, MD, USA; BRIAN DROUIN, Jet Propulsion Laboratory, California Institute of Technology, Pasadena, CA, USA; MITCHIO OKUMURA, Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, CA, USA.

Accurate spectroscopic models are required for remote sensing missions that use spectroscopic methods to interrogate atmospheric composition. The oxygen A-band (762 nm) is utilized for determination of air mass, solar pathlength and surface pressure in remote sensing applications due to the uniform concentration of molecular oxygen throughout the atmosphere and the spectral isolation of the band. NASA’s OCO-2 satellite seeks to retrieve atmospheric carbon dioxide concentrations with an accuracy of 0.25%, placing stringent demands on our knowledge of the A-band spectral parameters. Current limitations in the A-band spectroscopic models, primarily from the treatment of line mixing (LM) and collision induced absorption (CIA), FE01 8:30 – 8:45 remain a significant source of error in carbon dioxide column retrievals. LM is manifested as an intensity exchange due to ORIENTATIONAL ANISOTROPY INDUCED INHOMOGENEOUS LINE BROADENING IN THE ROVIBRATIONAL collisional population transfer between closely spaced energy levels while CIA appears as a broad, weak continuum absorp- SPECTRA OF CYANOACETYLENE SOLVATED IN HELIUM DROPLETS, OR: HOW I LEARNED TO STOP WORRY- tion feature arising from transient dipoles induced by molecular collisions. Photoacoustic spectroscopy, a zero-background ING AND LOVE THE PROVERBIAL DROPLET EFFECTS technique with a large dynamic range, is an ideal method to observe these effects which become increasingly prominent at elevated pressures. We have developed a high precision (SNR 10,000), broadband photoacoustic spectrometer for recording PETER R. FRANKE, GARY E. DOUBERLY, Department of Chemistry, University of Georgia, Athens, GA, full A-band spectra at room temperature over a wide range of pressures (300-3000 Torr). Intensity exchange due to LM USA. is observed in these unsaturated, high SNR spectra, and the weak baseline CIA profile can be extracted without interfer- ences from instrumental background effects. Results from multispectrum fits of this data with non-Voigt line shapes showing Strongly J-dependent inhomogeneous line broadening effects are observed in the zero-field rovibrational spectrum of insufficiencies in current A-band models will be presented. HCCCN solvated in superfluid helium droplets. We have attempted to simulate this broadening via the application of a model that accounts for the coupling of translational and rotational motion that arises from the anisotropic nature of the molecule- helium interaction potential as the impurity is displaced from the droplet’s center of mass. FE04 9:24 – 9:39 FT-IR MEASUREMENTS OF O2 COLLISION-INDUCED ABSORPTION IN THE 565 – 700 NM REGION USING A HIGH PRESSURE GAS ABSORPTION CELL

KEEYOON SUNG, Jet Propulsion Laboratory, California Institute of Technology, Pasadena, CA, USA;ED- WARD H WISHNOW, Space Sciences Laboratory and Department of Physics, University of California, Berkeley, CA, USA; TIMOTHY J. CRAWFORD, DEACON J NEMCHICK, BRIAN DROUIN, SHANSHAN YU, VIVIENNE H PAYNE, Jet Propulsion Laboratory, California Institute of Technology, Pasadena, CA, USA; JONATHAN H JIANG, Science Diviion, Jet Propulsion Laboratory, California Institute of Technology, Pasadena, CA, USA. FE02 8:48 – 9:03 The collision-induced absorptions (CIA) of O2 and dry air were measured in the near-infrared and visible region, cov- ULTRAVIOLET SPECTROSCOPY OF SUPERCRITICAL CARBON DIOXIDE ering the O2 B-band at 687 nm and double transitions in the 630 and 577 nm region. A newly customized 1 m pathlength high-pressure cell was developed and configured to a Fourier transform spectrometer, Bruker 125HR, at the Jet Propulsion TIMOTHY W MARIN, Physical Science, Benedictine University, Lisle, IL, USA; IRENEUSZ JANIK, Radiation Laboratory. A super luminous cutting-edge Laser-Driven Light Source (LDLS), was also used to improve the photon flux of- Laboratory, University of Notre Dame, Notre Dame, IN, USA. fered by the spectrometer. A series of spectra of pure O2 and dry air were obtained at various pressures up to 131 bars at room Vacuum ultraviolet spectroscopy was used to explore the density dependence of supercritical carbon dioxide electronic temperature. For the CIA of O2 B-band region, the monomer resonance absorption contribution to the observed spectra has absorption spectra over the wavelength range 145.5-200 nm at 34.5 ◦C. Pressure was varied from 19 to 137 bar, giving a been subtracted by simulating their absorption with a speed-dependent Voigt line shape profile with line mixing effects taken corresponding density range of 0.036-0.767 g cm−3. The vibronic structure inherent to the spectrum is apparent at the lowest into account. The remaining absorption component was interpreted as the CIA component in the region. The integrated ab- −3 × −4 −1 2 densities, but gradually diminishes in magnitude with increasing density. At a density of 0.595 g cm the structure is no sorption coefficient was measured to be 0.024(6) 10 cm /Amag for the O2 B-band region, which are significantly lower longer apparent. This loss of detail cannot be explained by collisional broadening or dimerization, and we suggest gradual than early measurements. For the two double transition bands in the 630 and 577 nm regions, however, the integrated CIA × −4 −2 2 perturbation of the monomer electronic and vibrational structure with increasing density, similar to that observed in recent from this work were measured to be 2.50(14) and 3.17(18) 10 cm /Amag , respectively, which are significantly higher than their corresponding early measurements. For dry air, the integrated CIA were measured to be 0.10(2) and 0.15(2)×10−4 studies of supercritical water. −2 2 cm /Amag , respectively, for the 630 and 577 nm region, with no appreciable contribution from the O2-N2 pairs in this work. The results are compiled in electronic supplements.& & Government sponsorship acknowledged. 232 233

FE05 9:42 – 9:57 FE07 10:54 – 11:09 NUMERICAL EVALUATION OF HARTMANN-TRAN LINE PROFILE USE IN SYNTHETIC, NOISY SPECTRA HIGH-ACCURACY HIGH-TEMPERATURE PRESSURE BROADENING AND LINE POSITIONS FOR MODELING H O 2 AND CH4 IN EXOPLANET ATMOSPHERES ERIN M. ADKINS, JOSEPH T. HODGES, Material Measurement Laboratory, National Institute of Standards and Technology, Gaithersburg, MD, USA. EHSAN GHARIB-NEZHAD, School of Molecular Sciences, Arizona State University, Tempe, AZ, USA;ALAN HEAYS, JAMES R LYONS, MICHAEL R LINE, School of Earth and Space Exploration, Arizona State Univer- Although the Voigt profile (VP) has long been used as a standard spectroscopic line profile, more stringent demands sity, Tempe, AZ, USA; HANS A BECHTEL, Advanced Light Source, Lawrence Berkeley National Laboratory, in high-resolution spectroscopy now require the application of other profiles that account for physics not captured by the Berkeley, CA, 94720, USA. VP. The Hartmann-Tran Profile (HTP) [1] was recommended by an IUPAC task group to be a standard for high-resolution H O spectroscopy because it parameterizes higher-order physical effects, is computationally efficient, and reduces to the VP and Infrared line positions and pressure-broadening data of atmospheric key absorbers 2 and CH4 strongly impact the in- other widely used profiles as limiting cases [2]. As advanced line profiles such as the HTP are adopted by more researchers to terpretation of exoplanetary observational data. The inaccuracy of absorption cross-sections (opacity data) biases atmospheric model or predict absorption spectra, it is important to understand the limitations that data quality has on the ability to retrieve radiative transfer modeling. The detection of CH4, for instance, is still under debate, despite extensive endeavors to model physically meaningful parameters from least-squares fits of assumed profiles to measurements with finite signal-to-noise ratio the chemical composition of exoplanetary atmospheres. To this end, we are carrying out the following projects. (SNR). In this work, synthetic, noisy spectra were simulated using the HITRAN Application Programming Interface (HAPI) First, high-resolution high-temperature H2-pressure-broadened spectra are recorded for the CH4 ν3-band P-branch. Mea- [3] across a range of parameters, SNR, and spectral sampling interval. The HTP was fit to these spectra to determine how sured linewidths for 112 transitions between 2840 and 3000 cm−1 with temperature and pressures ranging between 300 and simulated conditions affect fitted parameter uncertainty and correlations between parameters. We also investigated under 700 K, and 10 and 933 Torr, respectively, were used to find rotation- and tetrahedral-symmetry-dependent coefficients for what circumstances and constraints the parameters derived from fitting the HTP adequately model the full HTP. pressure and temperature broadening and pressure-induced lineshifts. 1. Tran, H., N. Ngo, and J.-M. Hartmann, Efficient computation of some speed-dependent isolated line profiles. Journal Second, we are currently investigating the impact on H2O absorption cross-sections of various line lists (e.g., POKAZA- of Quantitative Spectroscopy and Radiative Transfer, 2013. 129: p. 199-203. TEL vs. BT2). We assess the potential bias when interpreting the cross-correlation function through Earth-based observations. 2. Tennyson, J., et al., Recommended isolated-line profile for representing high-resolution spectroscopic transitions We report our progress in measuring high-temperature H2O line positions. (IUPAC Technical Report). Pure and Applied Chemistry, 2014. 86(12): p. 1931-1943. 3. Kochanov, R.V., et al., HITRAN Application Programming Interface (HAPI): A comprehensive approach to working with spectroscopic data. Journal of Quantitative Spectroscopy and Radiative Transfer, 2016. 177: p. 15-30.

FE08 11:12 – 11:27 TEMPERATURE-DEPENDENCE OF SELF- AND AIR-BROADENED CO LINE SHAPES IN THE FUNDAMENTAL BAND

Intermission ADRIANA PREDOI-CROSS, NAZRUL ISLAM, Department of Physics and Astronomy, University of Leth- bridge, Lethbridge, Canada; MARY ANN H. SMITH, self-employed, Retired, Newport News, VA, USA;V. MALATHY DEVI, Department of Physics, College of William and Mary, Williamsburg, VA, USA;SERGEI VIVANOV,Institute on Laser and Information Technologies, Russian Academy of Sciences, Troitsk, Moscow, Russia; FRANCK THIBAULT, Institut de Physique de Rennes, Universite´ de Rennes 1, Rennes, France. FE06 10:36 – 10:51 ← HIGH TEMPERATURE METHANE LINE BROADENING BY H2 We present results of an extensive analysis of the CO 1 0 band in 40 spectra of pure carbon monoxide and carbon monoxide mixed with air recorded at temperatures ranging between 79 K and room temperature. All spectra were recorded MAHDI YOUSEFI, Department of Physics, Old Dominion University, Norfolk, VA, USA; PETER F. BERNATH, using the 1-m McMath-Pierce Fourier Transform spectrometer located at Kitt Peak, AZ, USA and two temperature-controlled MICHAEL DULICK, Department of Chemistry and Biochemistry, Old Dominion University, Norfolk, VA, USA. gas cells. The analysis was carried out using multispectrum fitting softwarea and the Voigt, speed-dependent Voigt and Rautian line shape models. When using the Rautian model, we employed calculated narrowing parameters obtained from computed −1 b Absorption spectra of hot methane were recorded in the 2300-3200 cm spectral region (ν3 mode) using a Bruker diffusion constants for each of the absorber-perturber pairs CO-CO, CO-N2 and CO-O2. The experimentally retrieved 120/125 HR Fourier transform spectrometer. Methane was heated in a quartz cell in a tube furnace at 295, 473, 673, 873 and temperature dependences of the line shape parameters are been compared with previous published results and with the results 1073 K. Line broadening of the methane spectra was investigated by adding 50, 150 and 400 Torr of H2 as a broadening gas of calculations for CO-N2. to 0.5 Torr of methane. A preliminary spectral fit of the methane data was performed using Voigt line shape functions with We thank D. Chris Benner for the Labfit software. The work of V. M. Devi was funded by NASA grants and contracts, the WSpectra program. The temperature and pressure dependence of the line broadening parameters were studied; additional and the research by M. A. H. Smith was performed as part of her former employment at NASA Langley Research Center. No spectra are needed for more temperatures and pressures. A more sophisticated analysis using non-Voigt line shapes and a official endorsements are intended or implied. N. Islam and A. Predoi-Cross have been funded by NSERC. S. Ivanov received multi-spectral fit will be carried out. financial support from the Ministry of Science and Higher Education within the State assignment FSRC ”Crystallography and Photonics” RAS and Russian Science Foundation (Project No.18-55-16006).

aD. C. Benner, C. P. Rinsland, V. Malathy Devi, M. A. H. Smith and D. A. Atkins, JQSRT 53 (1995) 705-721. bJ. O. Hirschfelder, C. F. Curtiss and R. B. Bird, Molecular theory of gases and liquids, New York, Wiley and Sons, 1952. 234 235 FF. Comparing theory and experiment FE09 11:30 – 11:45 Friday, June 21, 2019 – 8:30 AM INVESTIGATION OF ORTHO-PARA-DEPENDENT PRESSURE BROADENING IN THE ν1 + ν3 BAND OF ACETY- LENE Room: 2079 Natural History

EISEN C. GROSS, TREVOR SEARS, Department of Chemistry, Stony Brook University, Stony Brook, NY, USA. Chair: Jinjun Liu, University of Louisville, Louisville, KY, USA

Several years ago, Iwakuni et al.1 reported an unexpectedly strong ortho-para-dependence to the self-pressure broadening in the ν1 + ν3 vibrational band of acetylene. Such an effect can arise because ortho-ortho collisions are statistically more probable than para-para ones and resonant energy transfer processes can make like-molecule collisions more efficient in state-changing, lifetime-shortening, collisions. Subsequently several papers23have disputed the observation on the basis that the experimental sensitivity could not be sufficient, and the approximate Voigt lineshape model used in the analysis FF01 8:30 – 8:45 would lead to systematic errors. However, there has been no reported independent experimental work to verify the results or investigate the refutations. Our group previously reported4 a very accurate and precise measurement of the self-pressure STRETCHING OUR KNOWLEDGE OF THE ELECTRONIC GROUND STATE OF C3: THE SPECTROSCOPY OF broadening for the P(11) transition in the same band, using a comb-stabilized laser spectrometer. We have now resurrected this STRETCHING MODES OF C3 instrument, and measured additional R-branch lines to investigate the controversial results described above. Measurements KIRSTIN D DONEYa, JILA and NIST, University of Colorado, Boulder, CO, USA;BENJAMINSCHRODER,¨ of the R(12)−R(15) transitions, which showed significant ortho-para differences in the original work, have been made at Institute of Physical Chemistry, Georg-August-Universitat¨ Gottingen,¨ Gottingen,¨ Germany; DONGFENG pressures ranging from 200 mTorr to 150 Torr. We fit the data to both Voigt and speed dependent Voigt (SDV) lineshape ZHAO, Hefei National Laboratory for Physical Science at Microscale, University of Science and Technology model to determine the pressure broadening coefficients and investigate their rotational and nuclear-spin dependence. of China, Hefei, China; PETER SEBALD, Institute of Physical Chemistry, Georg-August-Universitat¨ Gottingen,¨ Acknowledgment: This material is based upon work supported by the U.S. Department of Energy, Office of Science, Gottingen,¨ Germany; HAROLD LINNARTZ, Leiden Observatory, Sackler Laboratory for Astrophysics, Univer- Division of Chemical Sciences, Geosciences and Biosciences within the Office of Basic Energy Sciences, under Award siteit Leiden, Leiden, Netherlands. Number DE-SC0018950. 1. K. Iwakuni, S. Okubo, K. M. T. Yamada, H. Inaba, A. Onae, F.-L. Hong, and H. Sasada, Phys. Rev. Lett. 117, (2016). We present the high-resolution spectrum of C3 produced in a supersonically expanding propyne plasma, which is recorded 2. K. K. Lehmann, J. Chem. Phys. 146, 094309 (2017). around 3 μm using continuous wave cavity ring-down spectroscopy (cw-CRDS). Fifteen fully resolved ro-vibrational bands 3. J.-M. Hartmann and H. Tran, Phys. Rev. Lett. 119, (2017). are observed, which have been assigned to vibrationally excited nν1+mν3 combination bands of C3; fourteen of which are 4. M. J. Cich, C. P. McRaven, G. V. Lopez, T. J. Sears, D. Hurtmans, and A. W. Mantz, Appl. Phys. B. 109, 373 (2012). reported for the first time. This work is a significant extension of the known electronic ground state vibrational energy levels, with the observed number of quanta being: n ≤ 7andm≤ 3. Furthermore, with the new observations of highly excited vibrational modes, up to the (7,0,1) energy level, we are able to test the fundamental understanding of this ”floppy” benchmark molecule. A detailed analysis of the experimental spectra is supported by ro-vibrational calculations based on an ˜ 1Σ+ b accurate local ab initio potential energy surface (PES) for C3 (X g ). The presented variational calculations give remarkable agreement compared to experimental values with typical accuracies of ∼0.01% for the vibrational frequencies and ∼0.001% for the rotational parameters, even for high energy levels around 10000 cm−1.c

aPreviously at Universiteit Leiden (Sackler Laboratory for Astrophysics). bB. Schroder¨ and P. Sebald, J. Chem. Phys. 144, 044307 (2016) cB. Schroder¨ et al., J. Chem. Phys. 149, 014302 (2018)

FF02 8:48 – 9:03 MOMENTUM DICTATES INTENSITY: UNUSUAL OBSERVATIONS IN PHOTOELECTRON SPECTROSCOPY

JARRETT MASON, JOSEY E TOPOLSKI, JOSHUA C EWIGLEBEN, SRINIVASAN S. IYENGAR, CARO- LINE CHICK JARROLD, Department of Chemistry, Indiana University, Bloomington, IN, USA.

− Striking variations in excited state band intensities were observed in the photoelectron spectra of Sm2O collected using eight different photon energies. The spectra exhibit a pronounced overall increase in excited state band intensities relative to the transition to the ground neutral state as the photon energy decreases. This anomaly opposes that which would be expected to arise from threshold effects. The photoelectron spectra of several homonuclear Sm and heteronuclear Sm-Ce oxides collected previously with the second and third harmonic outputs of a Nd:YAG (2.33 eV and 3.49 eV) reveal a similar relationship, making the likelihood of coincidental resonance seem remote. Moreover, the absence of this phenomenon in homonuclear Ce-based clusters implicates the exceptionally high density of accessible spin states originating from the partially-filled 4f subshell of Sm. In addition, a broad oscillation in plots of the relative band intensities versus electron kinetic energy may map onto quasibound states of the anion. The results presented bear significance in the study of other electron-rich systems and models the interaction of the photoelectron and remnant neutral-like species. 236 237

FF03 9:06 – 9:21 FF05 9:42 – 9:57 MODELING ELECTRON DETACHMENT FROM METAL OXIDE CLUSTERS WITH EFFICIENT ELECTRONIC ANALYZING THE ROTATIONAL AND SPIN STRUCTURE OF THE TWO LOWEST ELECTRONIC STATES OF STRUCTURE METHODS ASYMMETRICALLY SUBSTITUTED ALKOXY RADICALS

HRANT P HRATCHIAN, Chemistry and Chemical Biology, University of California Merced, Merced, CA, USA. YI YAN, TERRY A. MILLER, Department of Chemistry and Biochemistry, The Ohio State University, Colum- bus, OH, USA; JINJUN LIU, Department of Chemistry, University of Louisville, Louisville, KY, USA. Photoelectron spectroscopy is a powerful technique for investigating the structure and reactivity of metal oxide clusters, which can serve as models of surface defect sites. Assigning photoelectron spectra typically requires corroborating computa- The members of the alkoxy radical family play important roles in oxidation processes, both in combustion and the ˜ 2 tional simulations. Motivated by the complicated electronic structure often exhibited by these species that can challenge the atmosphere, and their spectrocopy is well studied. The simplest species, CH3O, has a degenerate X E ground electronic quality of computational results using widely available quantum chemistry methods, our group has explored the development state, which has a near-UV transition to a non-degenerate electronic state presently referred to as B˜2A. Larger family members of efficient electronic structure models to describe photodetachment. This talk will describe these efforts and our lab’s recent formed by alkyl group substitution of the H atom(s) shift the A˜-X˜ electronic transition to the red as the size of the alkyl group applications of such models in investigations of various metal oxide clusters. grows. If the H atom(s) substitution is not symmetric, the degeneracy of the X˜ state is resolved into two non-degenerate ˜ ˜ electronic states, presently referred to as X and A. Typically the energy separation, ΔE0, between these two states, caused by the vibronic quenching mechanisma,b,issmall(≤ 1000cm−1). Historically, the approach to the spectra involving these three states has been to analyze the rotational structure in the X˜ and A˜ states separately via a Hamiltonian including an asymmetric top rotational term and a spin-rotation interaction. Recently Liuc has suggested that, as is done with the X˜ 2E state of methoxy, ˜ ˜ the structure of both the X and A states, now separated by ΔE0, and coupled by the spin-orbit and Coriolis interactions, is better considered together. This “coupled two-state model” also allows semi-quantitative prediction of effective spin-rotation constants using calculated molecular geometry and spin-orbit constants, which can be calculated with considerable accuracy. In the present work, we have simulated rotationally and fine-structure resolved laser-induced fluorescence (LIF) spectra of alkoxy radicals with the Liu model and fit the rotational constants, as well as the spin-orbit and Coriolis coupling parameters between the A˜ and X˜ states, holding the spin-rotation parameters at zero. The fits have been carried out for ethoxy, 2 conformers of propoxy, and 4 conformers of butoxy. Comparisons between the experimental spectra and simulations with both models (with separated and coupled electronic states) will be shown and relationships between the parameters from both models will be discussed.

aR. Renner, Z. Phys. 92, 172 (1934). bD. A. Mills, C. M. Western, and B. J. Howard, J. Phys. Chem. 90, 3331 (1986) cJ. Liu, J. Chem. Phys. 148, 124112 (2018).

FF04 9:24 – 9:39 Intermission 12 NON-RESONANT RAMAN SPECTRA OF THE METHYL RADICAL CH3 SIMULATED IN VARIATIONAL CALCU- LATIONS

AHMAD Y. ADAM, Faculty of Mathematics and Natural Sciences, University of Wuppertal, Wuppertal, Ger- FF06 10:36 – 10:51 many; ANDREY YACHMENEV, Center for Free-Electron Laser Science (CFEL), Deutsches Elektronen- ANALYSIS OF PSEUDO-JAHN-TELLER EFFECT IN METAL ALKOXIDES Synchrotron (DESY), Hamburg, Germany; SERGEI N. YURCHENKO, Department of Physics and Astronomy, University College London, Gower Street, London WC1E 6BT, United Kingdom;PERJENSEN, Faculty of Math- KETAN SHARMA, TERRY A. MILLER, Department of Chemistry and Biochemistry, The Ohio State Univer- ematics and Natural Sciences, University of Wuppertal, Wuppertal, Germany. sity, Columbus, OH, USA; ANAM C. PAUL, JINJUN LIU, Department of Chemistry, University of Louisville, Louisville, KY, USA. 12 We report first-principles variational simulation of the non-resonant Raman spectrum for methyl radical ( CH3)inthe electronic ground state. Calculations are based on a high level ab initio potential energy and polarizability tensor surfaces The proposed possibility of laser cooling of alkaline earth monoalkyl (MR) and monoalkoxide (MOR) free radicals, 3 3 of CH3 and employ accurate variational treatment of the ro-vibrational dynamics implemented in the general code TROVE e.g. CaCH and CaOCH , has generated significant experimental interest in the spectroscopic analysis of these open-shell [S. N. Yurchenko, W. Thiel, and P. Jensen, J. Mol. Spectrosc. 245, 126–140 (2007); A. Yachmenev and S. N. Yurchenko, J. molecules with orbitally degenerate or nearly degenerate low-lying electronic states. The analysis of laser induced fluores- Chem. Phys. 143, 014105 (2015)]. We extend the capabilities of TROVE towards simulations of the Raman spectra, which cence (LIF) and dispersed fluorescence (DF) spectra of such molecules requires an in-depth analysis of couplings between can in be applied to arbitrary molecule of moderate size. The simulations for CH3 are found to be in a good agreement with close lying electronic states. The Jahn-Teller and psuedo-Jahn-Teller effect plays an important role in the spectra of these the available experimental data. molecules. The molecular interaction picture is even more complex due to the presence of spin-orbit couplings between electronic states. In this talk we present our methodology for treating psuedo Jahn-Teller couplings for calcium methoxide (CaOCH3), calcium ethoxide (CaOC2H5) and calcium iso-propoxide (iso-CaOC3H7). A combination of EOM-CCSD and multi-mode Spin-Vibronic calculations have been employed to calculate transition frequencies and intensities for the exci- tation and emission spectra of these molecules. These calculations are used to understand the LIF and DF spectra, and to predict the feasibility of laser cooling of these molecules. 238 239

FF07 10:54 – 11:09 AUTHOR INDEX CALCULATING ROTATIONAL SIGNATURES FOR JAHN-TELLER DISTORTED MOLECULES Baraban, Joshua H – TJ01, TL10 Brogan, Crystal L. – WG05, RA01 KETAN SHARMA, Department of Chemistry and Biochemistry, The Ohio State University, Columbus, OH, A Barclay, A. J. – WB02, WH02, WH04, Bross, David H. – WD05 USA; SCOTT M. GARNER, Department of Chemistry, University of California at Berkeley, Berkeley, CA, USA; WH06 Bruckhuisen, Jonas – FB05 TERRY A. MILLER, Department of Chemistry and Biochemistry, The Ohio State University, Columbus, OH, Abadi, Sakineh E.M. – TL09 Barger, Christopher J – WG04 Brunken,¨ Sandra – WF04, WF05 USA; JOHN F. STANTON, Physical Chemistry, University of Florida, Gainesville, FL, USA. Abdelkader Khedaoui, Omar – TA02, Barnum, Timothy J – TE04, TH10 Buchanan, Zachary – MJ09, MJ10, WC01 Basnayake, Gihan – TF04, WC04, WG06 A Jahn-Teller active molecule demonstrates a characteristic signature in its rotationally resolved spectra due to the dis- RL09 Bui, Thinh Quoc – FE03 tortions from the symmetric configuration. In the past decades, this signature has been used to experimentally access and Ablaberdieva, Angela – TH03 Abplanalp, Matthew James – TA07 Bauerecker, Sigurd – MI04, MI05 Bunn, Hayley – TA05 understand the dynamics around a conical intersection. In this talk we present a method to calculate this rotational signature Baugh, Kira – WI10 Burevschi, Ecaterina – TB01, TB06, starting with electronic structure calculations. We derive an Effective Rotational Hamiltonian (ERH) for Jahn-Teller active Adam, Ahmad Y. – FA07, FF04 Adam, Allan G. – TI03, TI05, RL08 Baumann, Esther – FB02 RH06 systems and determine the relationship between the experimentally observable rotational parameters and electronic structure Beaman, Craig W. – MI06 Burggraf, Larry W – WA02 theory. The methodology has been further extended to include molecules with significant spin-orbit interaction. We have Adamovich, Igor V. – TL08 Adkins, Erin M. – RJ04, FE05 Bechtel, Hans A – FE07 Burkhardt, Andrew M – WG08 calculated both h1, which manifests from distortions in the plane perpendicular to the highest symmetry rotational axis of the Aitken, R. Alan – MH04 Beck, Martin – WD02 Burton, Mark – WJ07 molecule, and h2, which manifests from out-of-plane distortions of the molecule. We present our findings for cyclopentadi- Alekseev, E. A. – MI04, MI05, RG08, Becker, Andreas – WE07, RK02, Butler, Jake – WI10 enyl (C5H5), methoxy (CH3O) and nitrate (NO3) radicals and compare them to experimental data available in the literature. FB04 RK08 These calculations not only help guide experiments but are also a great tool for benchmarking high-level quantum chemistry Bekhtereva, Elena – MI04 calculations. Alikhani, Esma¨ıl – WJ09 C Alkorta, Ibon – MH07 Belkhodja, Yacine – WH01, FB05 Alonso, Elena R. – TB01, TG02, TJ07, Bell, Aimee – FA04 Cabezas, Carlos – TA08, TG06, TG07, FF08 11:12 – 11:27 RG04, RG08 Belloche, Arnaud – MG04 RJ05 TUNNELING REACTIONS OF HYDROGEN ADDITION TO PROPENE IN A SOLID PARA-HYDROGEN MATRIX Alonso, Jose´ L. – TG02, TJ07, RG04 Benidar, Abdessamad – TA02, WC01 Calabrese, Camilla – TB05, TC02, Alonso, Maria – WC07, FB06 Benke, Kristopher – WK07, RK03 WG09 GREGORY T. PULLEN, PETER R. FRANKE, GARY E. DOUBERLY, Department of Chemistry, University of Amari, Sachiko – WA01 Benston, Hannah N – WL09 Caminati, Walther – MH06 Georgia, Athens, GA, USA; KAROLINA ANNA HAUPA, Applied Chemistry, National Chiao Tung University, Amiaud, Lionel – RK04 Berger, Yann – WH01, FB05 Campargue, Alain – WA07 Hsinchu, Taiwan; YUAN-PERN LEE, Applied Chemistry, National Chiao Tung University, Hsinchu, Taiwan, Amicangelo, Jay C. – WH08, FD01 Bermudez,´ Celina – TA08, TG06, Cao, Wenjin – WF09 Institute of Atomic and Molecular Sciences, Academia Sinica, Taipei, Taiwan. Ampadu Boateng, Derrick – TF02, TG07 Cardinaud, Charlotte – MH04 TF03 Bermudez´ Montana,˜ Marisol – ML10 Carroll, Brandon – MG06, RG05, We report the branching ratio for the H + propene tunneling reaction to form n-ori-propyl radicals within a solid para- Anderson, David T. – TF08, TF09 Bernal, Jacob – WA01, WA03 RI04, FB01 H H hydrogen (p- 2) matrix at 3.2 K. Chlorine and propene are co-deposited in the p- 2 matrix, and then 365 nm and infrared Antonov, Ivan – TD09 Bernard, Jate W. – MH03 Carvajal, Miguel – ML10 light sources are used to produce HCl and free H atoms. These free H atoms can tunnel through the matrix until they encounter Araki, Mitsunori – MG03, FA01 Bernath, Peter F. – WA04, WA08, Cernicharo, Jose – TA08, TG02, a propene molecule, at which point they can react to form either an n-propyl or an i-propyl radical. i-Propyl was produced in Arenas, Benjamin E – TA03 RJ01, RJ02, FE06 TG06, TG07, RG08 greater proportion than n-propyl, indicating that for hydrogen addition to the double bond, the rate of addition to the terminal Ariyaratne, Tulana – TC03 Biczysko, Malgorzata – ML06 Chakraborty, Tapas – WB08, FC06 carbon (i-propyl) is faster than the rate of addition to the center carbon (n-propyl). Because the barriers for addition are Arsenault, Eric A. – WI07 Biennier, Ludovic – TA02, WC01 Champenois, Elio G – TK09 −1 −1 H approximately 700 cm – 1500 cm (1000 K – 2000 K), the only available mechanism for reaction in the p- 2 matrix Ash, Ryan T – WE02, RK03 Billinghurst, Brant E. – MI06, ML04, Chance, Kelly – RJ03 (3.2 K) is tunneling. Ab initio calculations were used to compute the tunneling probabilities for the formation of the n-propyl Asselin, Pierre – TJ01, WH01, FB05 TJ01, WA04, WA08, FA04 Chang, M.-C. Frank – WC07, FB06 and i-propyl radicals. The rate of addition to the terminal carbon (i-propyl) was calculated to be faster, in agreement with Asthagiri, Aravind – WK03 Biswas, Somnath – TK05, TK08, Changala, Bryan – TJ01, TL10 experiment. Asvany, Oskar – WF02, WF04, WF05 WE03, WK03, WK06 Charnley, Steven B – WG08 Augenbraun, Benjamin – TE08 Biswas, Souvick – WB08, FC06 Chatterjee, Piyali – FC06 Awatsu, Minami – TG04 Bittner, Dror M. – WA08 Chattopadhyay, Goutam – FB06 Blake, Geoffrey – MG06, MJ06, Chen, Peter – WB06 B MK10, RG05 Chen, Peter – RL04 Blake, Thomas A. – TJ02, TJ03 Chen, TzuLing – RL06 Blodgett, Karl N. – ML07, TJ08, TJ10, Baba, Masaaki – MI08, MJ04, WD07 Chen, Yang – TD01 WI02 Babin, Mark C – TD06 Chen, Yu-Shan M. – FA03 Bocquet, Robin – MJ09 Bailey, William C. – TJ04 Chen, Zaijun – MJ02 Boone, Chris – RJ01, RJ02 Baker, Robert – TK01, TK05, TK06, Cheng, Austin – WI10 Bornhauser, Peter – WD02 TK08, WE03, WH05, WK03, Cheng, Chuan – RK06 Boudon, Vincent – WA07, FA05, WK06 Cheng, Cunfeng – ML09, TE03 FB08 Bakhmat, Yan – MI04 Cheng, Lan – MK02, MK08, TJ04 Bouledroua, M. – RJ09 Bales, Kristin N – WJ04, WJ05 Chernyak, Yury – TC06 Boye-P´ eronne,´ S. – TG03 Banawoe, Gaetan – WI10 Chick Jarrold, Caroline – TC07, FC05, Brauer, Carolyn – TJ02, TJ03 Bandaranayake, Savini Sandunika – FD07, FD08, FF02 Breier, Alexander A. – WA05, RG06 WH05, WK06 Chitarra, Olivia – WG06 Bres,` Camille-Sophie – MJ01 Banerjee, Sneha – TB09, WB10 Chmielinski, Alexander – TL07 Bresler, Sean Michael – WC10 Banhatti, Shreyak – WF05 Chou, Chin-wen – TE02 Broderick, Bernadette M. – TF06 Chowdhury, Farhan – TL09 240 241

Chrostowska, Anna – WD10 Dodson, Leah G – WF10 TI02 Gordon, Iouli E – WD03, RJ03 Heitkamper,¨ Juliane – MH08, MI01 Chung, Angela Y. – WI07 Domenech,´ Jose´ Luis – TA08, TG06, Fillmore, Kaycee L. – TF09 Goswami, Rapti – WB10 Herbst, Eric – WG08 Jackson, William M. – WD04 Chung, Chen-An – RJ06, RJ07 TG07 Fiorini, Anna – TC02 Gottlieb, Carl A – RI03 Herman, Daniel I. – FB02 Jaffe, Noah B – WJ06 Cich, Matthew J. – FE03 Domingos, Sergio R – RH01, RH02 Fischer, Joshua L. – ML07, TJ08, Gou, Qian – MH06 Herman, Tyler J – WJ08 Jager,¨ Wolfgang – MH09, WB03 Cirri, Anthony – FC08 Doney, Kirstin D – ML01, ML02, WI02 Goubet, Manuel – MI05, TJ01 Hernandez, Jose´ Manuel – TG07 Janik, Ireneusz – TD08, FE02 Clement, Mathew – WK03 TD05, FB07, FF01 Fischer, Kaitlyn C – TH08 Gougoula, Eva – MH07, MH08, MI01 Herrero, Victor Jose – TA08, TG06, Jans, Elijah R – TL08 Clouthier, Dennis – TD02, TD04 Donnell, Kristen – WC05 Flagey, Nicolas – WA06 Gozem, Samer – TA07 TG07 Jaraiz, Martin – RH08 Coburn, Sean – TI09 Dore, Jacob M – TI03, TI05 Flaud, Jean-Marie – ML04 Grabow, Jens-Uwe – MH06, TE07, Hewett, Daniel M. – TH03, WA04, Jaron-Becker, Agnieszka – WE05, Cocinero, Emilio J. – TC02 Dorman, P. Matisha – RI08 Fleisher, Adam J. – RJ04 RH04 WA08 WE07, RK02, RK05, RK08 Coddington, Ian – FB02 Dorovskaya, Olga – MI05, TG05, Fleurbaey, Helene M – RJ04 Grimes, David – TF10 Hindle, Francis – MJ09, MJ10 Jee, Jo-Ann – WL08 Cole, Ryan K. – RL03 RG08 Flores, Jonathan – FD05, FD06 Groner, Peter – MI03 Ho,PaulT.P.–WG03 Jennings, Don – WA08 Colley, Jason E. – WH10 Douberly, Gary E. – TE06, WF06, Foguel, Lidor – MI09 Gross, Eisen C. – FE09 Hodges, Joseph T. – MJ03, RJ04, Jensen, Per – FA07, FF04 Collopy, Alejandra – TE02 FE01, FF08 Folluo, Carley N – TC07, FC05 Grubbs II, G. S. – MA04, MI02, FE03, FE05 Jewell, Philip – MG08 Conway, Eamon K – WD03, RJ03 Doyle, John M. – MA01, TE08 Foltynowicz, Aleksandra – RA04 WC05, WC08, WC09, WI09 Hoghooghi, Nazanin – RL03 Ji, Zhonghua – TE01, RI10 Cooke, Ilsa Rose – TA02, WC01 Drouin, Brian – TI09, WC07, RA02, Fortier, Tara – TE02 Gruet, Sebastien´ – TA03, RA03 Holdren, Martin S. – WL01, WL03, Jia, Suotang – RI10 Cooke, S. A. – MI02, TJ02, TJ03, FB06, FE03, FE04 Foschini, Luca – TC02 Grzywacz, Robert – ML04 WL04, WL07 Jiang, Jonathan H – FE04 TJ04, WI07, WI08 Duan, Xiaofeng F – WA02 Foy, Brent D – WL09 Gu, Mingming – RL05 Holland, Torrey E. – WI01 Jiang, Jun – TE04 Cordiner, Martin – WG08 Dudek, John B – TC06 Francisco, Joseph S – TH01 Guillaume, Theo – TA02, WC01 Holt, Jennifer – WL10 Jimenez-Hoyos, Carlos A – WI07 Cordones-Hahn, Amy – TK09 Duerden, Amanda Jo – WC05, WC08, Franke, Peter R. – WF06, FE01, FF08 Guillemin, J.-C. – TG02, TG03, TG05, Holzwarth, R. – MJ01 Jin, Jiaye – TE05 Cossel, Kevin C – FB02 WC09 Frederickson, Kraig – TL08 TG08, RG07, RG08 Hoque, Laboni – TB07 Jin, Yan – MH06 Coudert, L. H. – TG03, RG09 Dulick, Michael – FE06 Friedlein, Jacob T – FB02 Gulaczyk, Iwona – TA01 Horness, Rachel E. – TF01 Johansen, Sommer L. – WG07 Coustenis, Athena – WA07 Duncan, Michael A – TH09, WF06, Fritz, Sean – TL02, WI06 Guo, Hairun – MJ01 Hossain, Umme H. – MH03 Johnson, Christopher J. – MA05, Coxon, John – TI02 WF08, WH10 Fuchs, Guido W – WA05, RG06 Gupta, Divita – TA02, WC01 Hougen, Jon T. – MI05, MI08, TA01 FC08 Coy, Stephen L – TH10 Dunkel, Emily – WC03 Fugate, Elizabeth A – TK08, WK03 Gupta, Harshal – WG02 Howe, Jane – WA01 Johnson, Dylan – WH08 Crabtree, Kyle N. – WC02, WD04, Dyott, Zachary – TH04 Fujii, Asuka – FC07 Gupton, B Frank – WL08 Hratchian, Hrant P – TC08, FF03 Johnson, Erika – MJ07 WG07 Fukushima, Masaru – TD07, WD09 Hruska, Emily B – TK06 Johnson, Mark – TH02 Crawford, Timothy J. – FE04 E Furuta, Jin – TI06 H Hsu, Cho-Wei – RJ07 Johnson, Rebecca N. – TA07 Crozet, Patrick – RL08 Hu, Changle – ML09 Jones, Ayanna – RG03 Cryan, James P – TK09 El-Abd, Samer – WG05 G Hadley, Kevyn – WI10 Hu, Ming-Guang – TF10 Jones, Walker Manley – MJ05 Cuisset, Arnaud – FB05 Eliet, Sophie – MJ09, MJ10 Haenecour, Pierre – WA01 Hu, Shui-Ming – ML09, TE03 Jorgensen, Jes – MG02 Cushing, Scott Kevin – TK07 Elles, Christopher G. – MJ08 Gallego, Juan Daniel – TA08, TG06, Hajigeorgiou, Photos – TI02 Hu, Xiye – TD10 Joyce, T – WE05, WE07, RK02, Ellison, Barney – TF07 TG07 Hande, Aniket – WD10 Hua, Tian-Peng – ML09 RK05 D Endo, Yasuki – RJ05, RJ06 Galvan-Madrid,´ Roberto – WG03 Hansch,¨ Theodor W. – MJ02 Huff, Anna – TB04, WB07, RI09 Juanes, Marcos – TB03, RH04, RH08 Engel, Franziska – TI04 Gans, B. – TG03 Hansel,¨ Wolfgang – MJ01 Humphreys, Roberta M. – WA03 Dagdigian, Paul – MK01 Enriquez, Lourdes – RH08 Garand, Etienne – ML05, TH08 Hansen, Kameron R – TK03 Hunter, Todd R. – WG05 K Daily, John W – TF07 Erickson, Blake A – WK04 Garcia,G.A.–TG03 Harb, Hassan – TC08 Huntington, Parker K – WL09, WL10 Daly, Adam M – MH04 Esselman, Brian J. – RI07, RI08, FA08 Garcia, Jacob M – TC04 Harman, W. Dean – MH03 Hurst, John – TL07 Kaiser, Catherine – WH08 Darrigan, Clovis – WD10 Esteki, Koorosh – WB02, WH02, Garner, Scott M. – FF07 Harms, Jack C – WJ01, WJ02, WJ04, Husek, Jakub – TK05, TK06, TK08, Kaiser, Ralf Ingo – TA07 Dattani, Nikesh S. – MK06, MK08, WH04 Garrod, Robin T. – MG04, WG04, WJ05 WE03 Kalambet, Mariia – MI05 FA06 Evangelisti, Luca – MH10, TB05, WG05 Harper,O.J.– TG03 Hutchings, Richard – ML04 Kalenskii, Sergei – WG08 Daunt, Stephen J. – ML04 TC02, WG09, WL01, WL02, Gauss, Jurgen¨ – TC06, TI04, WF05, Harrilal, Christopher P – TJ08, TJ09 Hutzler, Nicholas R – TE09 Kamegai, Kazuhisa – MG03 Dawes, Richard – TH06, TH07, WL06, WL08, RH04 RG06 Harris, Robert J – RG02 Kaminski, Tomasz – RG06 WD05, RJ08 Ewigleben, Joshua C – FF02 Gazali, Zainab – RL07 Harrison, Rachel E. – RG02 I Kanaoka, Ayumi – WD07 de Groot, Frank – RK03 Georges, Robert – TA02, TJ01, WA07, Hartwig, Beppo – MH05 Kannangara, Prashansa – TC03 de Oliveira, Nelson – FB09 F WC01 Hattori, Keigo – FC07 Ibrahim, Mohamad – WJ09 Karna, Priya – WJ10 de Vicente, Pablo – TG06 Gerber, R. Benny – TH02 Haupa, Karolina Anna – TA06, TD03, Ibrahim, Mohamed Amin – ML06 Karunanithy, Robinson – WI01 Debrah, Duke A. – TF04, WC04, Fairman, George – WI10 Gharib-Nezhad, Ehsan – FE07 FF08 Ilyushin, V. – MI04, MI05, TA01, Kasahara, Shunji – MJ04, WD08 RL09 Fatima, Mariyam – TB08, WB05 Gheorghe, Andrei – TF10 Havenith, Martina – FC02 TG05, RG08 Kasahara, Yasutoshi – FC03, FC04 Delaney, Thomas – TL07 Faulkner, Ty – WH07 Gibson, Stephen T – WF03, WF07, Hays, Brian M – TA02, WC01, WI06 Isert, Joshua E. – WI09 Kaszynski,´ Piotr – WD10 Dell’Isola, Valentina – FB01 Favero, Laura B. – TB05, WG09 FB09 Heald, Lauren F – WE08 Ishikawa, Haruki – FC03, FC04 Kataoka, Akimasa – RG02 Devi, V. Malathy – FE08 Federman, Steven – WA06, WD04 Giesen, Thomas – WA05, RG06 Hearne, Thomas Sandow – TA02, Ishiwata, Takashi – WD09 Kawashima, Yoshiyuki – WI03, WI04, DeVine, Jessalyn A. – TD06 Felder, Robin A. – TL07 Giorgetta, Fabrizio – FB02 WC01 Islam, Nazrul – FE08 WI05 Dewberry, Chris – WC03, WC06 Feng, Gang – MH06 Girolami, Gregory S. – RK03 Heaven, Michael – WC10, WD01, Ivanov, Sergei V – FE08 Keto, Eric – WG03 Dias, Nureshan – TF06 Fernandez,´ JoseA.–´ TB03 Goldsmith, Cory – WE07, RK08 WJ03, WJ06 Iyengar, Srinivasan S. – FF02 Khan-Rafii, Noah – TL07 Diddams, Scott – TE02 Fernando, Anton Madushanka – RJ02 Goldsmith, Paul F – WA06 Heays, Alan – FB09, FE07 Kim, Dongjoon – WK03 DiMauro, Louis – WE01 Field, Robert W – TE04, TH10, TI01, Gong, Ting – RI10 Heger, Matthias – MH09, WB03 J Kim, Hwihyun – WA06 Dobulis, Marissa A. – FD07, FD08 Gorbachev, Vladimir – WB06 Heim, Zachary N. – WK04 Kim, Jong Hyun – WJ10 242 243

Kim, Minkyu – WK03 Lee, Sean – WI10 Mellau, Georg Ch. – MI05 Nyambo, Silver – WJ10 Pinacho, Ruth – RH04 Kim, Yanghyo – WC07, FB06 Lee, Yuan-Pern – TA06, TD03, WD07, M Mendonca, Joseph – RJ04 Nyaupane, Parashu R – MJ05 Pintea, Maria – RK04 Kippenberg, Tobias J. – MJ01 RJ06, RJ07, FD01, FF08 Mengesha, Ephriem Tadesse – TE08, Pirali, Olivier – MI05, MJ09, MJ10, Kisiel, Zbigniew – TG02 Lees, Ronald M. – MI06 Ma, Xinwen – FD03 TE09 O TJ01, WG06, RG07, RG09 Klee, Bradley – RI06 Legon, Anthony – MH07 Mabbs, Richard – WF03 Menten, Karl M. – MG04 Pischer, Anna L – WC02 Kleimeier, N. Fabian – TA07 Lehmann, Kevin – TI10 Mace, Gregory N. – WA06 Meyer, Kelly S. – WC02 O’Brien, James J – WJ01, WJ02, Pitsevich, George – MI07 Kleiner, Isabelle – MI05, TA01 Lei, Shujun – TE05 Magdau, Ioan-Bogdan – MK10 Michaelian, K. H. – WH04 WJ04, WJ05 Pitts-McCoy, Anthony – TJ09 Kmiotek, Christina – FC08 Leibfried, Dietrich – TE02 Makowiecki, Amanda S. – RL03 Mikhonin, Alex – TL01, TL03, TL05 O’Brien, Leah C – WJ01, WJ02, Plunkett, Emily – TL07 Knopp, Gregor – WD02 Leibrandt, David – TE02 Malarich, Nathan A – TI09 Milam, Stefanie N – RG03 WJ04, WJ05 Poblotzki, Anja – WB05 Knowles, Nick – WC06 Leicht, Daniel – WF08 Malevich, Alex – MI07 Miller, Isaac James – WH07 Obenchain, Daniel A. – TB08, RH04 Polyansky, Oleg L. – WD03 Kobayashi, Kaori – TG04, TI06, TI07 Lemus, Renato – MK04, MK05, Manceron, Laurent – FB08 Miller, Terry A. – MK03, TL08, FF05, Oberg,¨ Karin I – WG03 Porterfield, Jessie P – TF07, TJ01, Kocheril, G. Stephen – RI03 ML10 Mandal, Pankaj – TB09, WB10 FF06, FF07 Ocola, Esther Juliana – WH03 TL10, FB01 Kolesnikova,´ Lucie – TG02, TJ07, Leon,´ Iker – RG04 Mandrell, Christopher – TL09 Miller, Thomas – TL07 Odom, Brian C. – TD09 Predoi-Cross, Adriana – FE08 RG04, RG08 Leopold, Kenneth R. – TB04, WB01, Mani, Devendra – FC02 Miller III, Thomas F. – MK10 Oka, Takeshi – FA02, FA03 Preston, Charles – TL07 Kopp, John K – WC06 WB07, RI09 Margules,` L. – MI05, TG05, TG08, Miloglyadova, Larisa – WB06 Okumura, Mitchio – FE03 Pringle, Wallace C. – WI07 Korslund, Hannah – MK08 Lesarri, Alberto – TB03, RH04, RH08 RG08, FB04 Minei, A. J. – WI08 Olenyik, Kelly M. – TF09 Pullen, Gregory T. – FF08 Kortyna, Andrew – ML02, TD05, Leung, Helen O. – TB02, TB07, Marin, Timothy W – FE02 Mishra, Hirdyesh – TA09, WB09 Orellana, W. – TJ02 Puzzarini, Cristina – MA03, TI04 FB07 RH02, RH03 Maris, Assimo – TB05, WG09 Mishra, Piyush – TL02, WI06 Orr, Vanessa L. – RI07 Kougias, Samuel M. – RI07 Lewen, Frank – MI04 Marks, Joshua H – TH09 Misono, Masatoshi – MI08, MJ04, Oslosky, Jacob – WH08 Q Kreglewski, Marek – TA01 Lewis, Brenton R – FB09 Markus, Charles R. – WF01, WF05 WD07 Owen, Andrew N – RI07 Kreuter, Florian – TI04 Li, Chuanliang – TE01 Marquardt, Roberto – WD02 Moazzen-Ahmadi, Nasser – WB02, Oyama, Takahiro – MG03, FA01 Quesada-Moreno, Mar´ıa Mar – RH05, Krin, Anna – RH02 Li, Weixing – TB05, RH07 Marshall, Frank E – MI02, WC05, WH02, WH04, WH06 Ozeki, Hiroyuki – TG04 RH07 Kroll, Jay A – MG07, TA04, TA05, Li, Wen – TF04, WC04, RK01, RL09 WI09 Momose, Munetake – RG02 Quintanilla, Jesus´ Eduardo – TA08, TC01 Li, Xiaolong – MH06 Marshall, Mark D. – TB02, TB07, Moon, Nicole – WC05, WC08, WC09 P TG07 Krueger, Ritter – TF06 Li, Zhi-Yun – RG02 RH02, RH03 Morales Hernandez, Hanna – FC08 Quintas Sanchez,´ Ernesto – TH06, Kukolich, Stephen G. – MH04 Li, Zhonghao – RI10 Moriwaki, Yoshiki – TI06 Martin-Drumel, Marie-Aline – MJ09, Pal, Nitish – FC02 TH07, WD05, RJ08 Kumar, Sanjay – TL04 Lin, Ming-Fu – RK03 Motiyenko, R. A. – MI05, TA01, MJ10, TI04, TJ01, WG06, Palmer, Michael H. – MH04 Kuroda, Shinji – WD08 Lin, Yiheng – TE02 TG05, TG08, RG08, FB04 WG07, RG07, RG09 Panchenko, Yurii – ML08 R Kurz, Christoph – TE02 Line, Michael R – FE07 Mouret, Gael¨ – MJ09, MJ10 Mason, Jarrett – TC07, FC05, FF02 Pang, Ran – TH05 Kuze, Nobuhiko – MG03, WI03, Linnartz, Harold – ML01, FF01 Muckle, Matt – TL01, TL03, TL05, Mason, Nigel – RK04 Pate, Brooks – MH03, MH10, TC02, Radi, Peter – WD02 WI04, WI05 Linton, Colan – TI03, TI05 WL08 Mata, Santiago – TJ07, RG04 TC03, TL07, WI10, WL01, Rai, A. K. – RL01, RL02, RL07 Kwabia Tchana, F. – FA05 Lipparini, Filippo – WF05 Mueanngern, Yutichai – WK03 Matsika, Spiridoula – RK06 WL02, WL03, WL04, WL05, Ramos, Sashary – TF01 Kwon, Woojin – RG02 Liu, An-Wen – ML09, TE03 Muller,¨ Holger S. P. – MG04, MI04 Matsumoto, Yoshiteru – FC04 WL06, WL07, WL08 Raston, Paul – WH07 Kyuberis, Aleksandra A. – WD03 Liu, Erica – WK04 Murphy, Keshihito J – WH09 Maul, Christof – MI04, MI05 Patrinely, Eleanor – WI10 Reber, Melanie A.R. – MJ05 Liu, Fang – TK03 Murugachandran, S. Indira – TB01 Mawhorter, Richard – TE07 Patros, Kellyn M. – FD07 Reck, Theodore J – FB06 Liu, Hauyu Baobab – WG03 Muto, Takayuki – RG02 L Mayer, Kevin J – MH10, WI10, Patterson, David – TL06, TL10 Redlich, Britta – FC02 Liu, Jinjun – TD10, TE01, FF05, FF06 Mutunga, Fredrick M. – TF09 WL01, WL05 Paul, Anam C. – TD10, FF06 Reed, Zachary – MJ03, RJ04 Liu, Junqiu – MJ01 Laane, Jaan – WH03 McCall, Benjamin J. – WF01 Payagala, Yudhishtara – WH08 Reiff, R – RK02 Liu, YiWei – RL06 Labbe, Nicole – TF07 McCarthy, Michael C – TH06, TH07, N Payne, Vivienne H – FE04 Reilly, Neil J – FD05, FD06 Liu, Yu – TF10 Lacy, John H. – WA06 TI04, TJ01, TL10, WG02, Pearson, John – WL07 Remijan, Anthony – MG01, MG08, Liu, Yuting – RI10 Lafferty, Walter – ML04 WG06, WG08, RG07, RI01, Nava, Matthew – TJ01 Pede, Chris A. – MH03 TG05, WG08 Loison, J.-C. – TG03 Lambert, David L. – WA06 RI02, RI03, RI04, FB01 Ndengue, Steve Alexandre – RJ08 Peebles, Rebecca A. – TC03 Reynolds, Roger L – TL01 Lombardo, Nicholas – WA08 Lampin, Jean-Franc¸ois – MJ09, MJ10 McCaslin, Laura M – TH02, FD06 Neese, Christopher F. – WL10 Peebles, Sean A. – TC03 Rice, Johnathan S – WA06 Londo, Stephen – TK05, TK08, WE03 Lasner, Zack – TE08 McDaniel, Dave – TL05 Negishi, Mayu – FA01 Pena,˜ Isabel – TB01, RH06 Richard, Cyril – FA05 Long, Brittany E. – MI02 Law, Charles John – WG03 McGuire, Brett A. – MG06, TG01, Neill, Justin L. – TL01, TL03, TL05, Perez, Cristobal – TB08, WB05, Rieker, Gregory B – TI09, RL03 Long, David A. – RJ04, FE03 Laws, Benjamin A – WF03, WF07 TG05, TI04, WG05, WG08 TL07, WL06, WL08 RA03, RH05, FC01 Riffe, Erika – MJ07 Loomis, Ryan – WG08 Le, Anh T. – TE08 McKellar, Bob – WB02, WH02, Nemchick, Deacon J – WC07, WL07, Perez-Bernal,´ Francisco Curro – ML10 Ritchey, Adam – WA06 Looney, Leslie – RG02 Le Picard, Sebastien D. – TA02, WH04, WH06 FB06, FE04 Persinger, Thomas D. – WJ03 Rittgers, Brandon M. – WF08 Lopez´ Perez,´ Jose´ Antonio – TG06 WC01 McLuckey, Scott A – TJ09 Nesbitt, David – ML02, TD05, FB07 Pert, Emmit – WI10 Rizopoulos, Athena – FA05 Loru, Donatella – TB01, TC05, RA03 Le Sueur, Amanda L – TF01 McMahon, Abbey – TC07, FC05 Neumark, Daniel – TD06, WK04 Petrov, Alexander – TE10 Rodr´ıguez Arcos, Marisol – MK04, Lovas, Frank J – MG08 Leahy, Clare – RK07 McMahon, Robert J. – RI07, RI08, Newbury, Nathan R. – FB02 Picque,´ Nathalie – MJ02 MK05 Love, Nathan – WB07, RI09 Lebron,´ Rosa – TA08, TG07 FA08 Newby, Josh – WH09 Pienkina, A. – TG08 Roenitz, Kevin – MG07, TC01 Lucht, Robert P. – TI08, RL05 Lee, Kelvin – TH06, TH07, TI04, Mead, Griffin – MJ06 Ng, Cheuk-Yiu – WD04 Pietropolli Charmet, Andrea – WB02, Rogers, Cory – TF07 Lunny, Elizabeth M – FE03 WG02, WG06, WG08, RG07, Medcraft, Chris – MH07, MH08, Ni, Kang-Kuen – TF10 WH06 Roper, Thomas D. – WL08 Luo, Nan – WD04 RI01, RI02, RI03, RI04, RI05, MI01, FB03 Nixon, Conor A – WA08 Pilgram, Nickolas – TE09 Ross, Amanda J. – RL08 Lutz, Jesse J – WA02 FB01 Medvedev, Ivan – WL09, WL10 Novick, Stewart E. – MH01, MH02, Pinacho, Pablo – TC05, RH05, RH07 Ross, Sederra D. – FD05, FD06 Lee, Sang – FD04 Lyons, James R – FB09, FE07 Melandri, Sonia – TB05, WG09 TJ02, TJ03, TJ04, WI07 244 245

Ross, Stephen Cary – TI06 Shari’ati, Yusef A. – WE04 Sung, Keeyoon – TI09, FE04 Tyuterev, Vladimir – WA07 Waxman, Eleanor – FB02 Ycas, Gabriel – FB02 Rothschopf, Gretchen K – TD04 Sharma, Aastha – TK02, TK04 Sur, Sangeeta – RJ08 Weber, J. Mathias – WF10 Yeh, Lia – TL06 Roy, P. – MJ09 Sharma, Ketan – MK03, FF06, FF07 Suzuki, Kojiro – WI05 U Weinacht, Thomas – RK06 Yi, Hongming – RJ04 Roy, Tarun Kumar – FC02 Sheridan, Phillip M. – WJ07 Svyda, Yu.Yu. – WD06 Welch, Bradley – WD05 Yocum, Katarina – RG03 Rubio, Jose´ Emiliano – RH04 Sherman, Summer Lee – TH08 Sydow, Christian – MI04, MI05 Uchida, Masaaki – FC04 Wells, Thresa – RL04 Yoshizawa, Seiya – WI03 Ruscic, Branko – WD05 Shields, George C – TC02, RA03 Sye, Kori – WK05 Ueda, Shoya – WD08 Wells, Tyler – WH07 Yousefi, Mahdi – FE06 Russ, Benjamin – WJ07 Shimizu, Takutoshi – FC04 Usabiaga, Imanol – TB05, WG09 Weng, Wenle – MJ01 Yu, Shanshan – WL07, FE04 Ryland, Elizabeth S – RK03, RK07 Shingledecker, Christopher N – WG08 T West, Channing – MH10, TC03, TL07, Yun, David – TI09 Shipman, Steven – MJ07 V WL01, WL02, WL05, WL06 Yurchenko, Sergei N. – WD03, FA07, S Sibert, Edwin – ML07, TH03, TH04 Takano, Shuro – MG03 Westerfield, J. H. – TL10, WC02 FF04 Signore, Joshua A. – TJ03, TJ04 Western, Colin – ML04 Yusef-Zadeh, Farhad – MG05 Takimoto, Takahiro – WI04 Vaccaro, Patrick – MI09 Silva, Weslley G. D. P. – TJ05, TJ06, Widicus Weaver, Susanna L. – MG07, Sagan, Cole R – ML05 Talhi, Fatima – RJ09 Vaida, Mihai E – WK02 WB04 TA04, TA05, TC01, RG03 Sakai, Nami – RG01 Tan, Yan – ML09 van der Meer, Lex – FC02 Z Simon, Ignacio – WI10 Wilkins, Olivia H. – RG05 Sakurai, Hidehiro – WD07 Tanarro, Isabel – TA08, TG06, TG07 van Wijngaarden, Jennifer – TJ05, Sims, Ian R. – TA02, WC01 Willis, Eric R. – MG04, WG05, WG08 Salomon, Thomas – TC06, WF02, Tang, Adrian – WC07, FB06 TJ06, WB04, FA04 Zagorec-Marks, Wyatt – WF10 Singh, Sandeep C – TL03 Wishnow, Edward H – FE04 WF05 Tang, Jackson – TB01 Vander Auwera, Jean – FA05 Zakharenko, Olena – MI04 Sivakumar, P – TL09, WI01 Witsch, Daniel – WA05 Sandhu, Arvinder – WK01 Tani, Iori – TI06 VanGundy, Robert A. – WJ03 Zandbergen, Patricia Vindel – RK06 Skripnikov, Leonid – TE10 Wolf, Thomas JA – TK09 Sanz, M. Eugenia – TB01, TB06, Tarczay, Gyorgy – ML06, TA06 Vastel, Charlotte – WG01 Zdanovskaia, Maria – FA08 Slawin, Alexandra M. Z. – MH04 Wong, Andy – WA04, WA08 RH06 Telfah, Hamzeh – TD10 Vealey, Zachary – MI09 Zega, Thomas J. – WA01 Smart, Taylor – WL01, WL03, WL04 Wong, Bryan M. – TH10 Sapeshka, Uladzimir – MI07 Temelso, Berhane – TC02, RA03 Venkataramanababu, Sruthi – TD09 Zerbini, Luca – TC02 Smith, CJ – TB04, WB07, RI09 Woods, R. Claude – RI07, RI08, FA08 Saragi, Rizalina Tama – TB03, RH04, Tennyson, Jonathan – RJ03 Venkataramani, Sugumar – FD02 Zhang, Deping – TD01 Smith,JacobA.–MH03 Woon, David E. – TG09 RH08 Tercero, Belen´ – TA08, TG07 Venzke, J – RK02, RK08 Zhang, Jicai – FD03 Smith, Mary Ann H. – FE08 Wright, Connor J. – MG07, TC01 Saraswat, Mayank – FD02 Tercero, Felix´ – TG06 Verkamp, Max A – TK02, TK04, Zhang, Kaili – WE02, RK03, RK07 Smith, Tony – TD02, TD04 Wu, Arthur – WL03, WL04 Sarkar, Sohini – TB09, WB10 Testoff, Thomas T – MK09 RK03 Zhang, Meng – RL10 Snyder, Lewis E. – MG08 Wu, De-Yin – TH05, RL10 Satija, Aman – TI08, RL05 Thakur, Surya Narayan – RL07 Voros, Tamas – ML06 Zhang, Qiang – TD01, WD02 Sogeke, Olamide P. – TJ05 Wu, Ruitao – MK07 Sato, Haruka – FA01 Thawoos, Shameemah – TF05 Voss, Jonathan – TH08 Zhang, Qizhou – WG03 Sonstrom, Reilly E. – MH03, MH10, Sato, Hikaru – FC03 Theis, Mallory – WJ06 Vura-Weis, Josh – TK01, TK02, Zhang, Yan – FB06 WL01, WL02, WL05, WL08 Satsunkevich, Valery – MI07 Thevenaz,´ Luc – MJ01 TK04, WE02, WE04, WK05, X Zhang, Yuchen – WF09, WJ10 Soria, Ana Cristina – TA08, TG07 Satterthwaite, Lincoln – TL06, TL10 Thibault, Franck – FE08 WK07, RK03, RK07 Zhang, Zitan – TE03 Saxena, Shefali – TB01 Soulard, Pascale – TJ01, WJ09 Thielges, Megan – TF01 Xiao, Liantuan – RI10 Zhao, Dongfeng – ML01, TD01, FF01 Stanton, John F. – MK01, MK03, Sayres, Scott G – TC04, TK01, WE06, Thomas, Javix – MH09 W Xie, Fan – MH09, WB03 Zhao, Jianbao – WA08 WE08 TD06, TJ01, FD06, FF07 Thompson, Michael C – FD07, FD08 Xu, Li-Hong – MI06 Zhao, Yanting – TE01, RI10 Schlemmer, Stephan – MI04, TC06, Stark, Glenn – FB09 Thorwirth, Sven – TC06, TI04, WF02, Xu, Yunjie – MH09, WB03 Zheng, Xuechen – MK02 Wagner, J. Philipp – WH10 TI04, WF02, WF04, WF05 Steber, Amanda – TA03, TC05, WF04 Xu, Zhongxing – WD04 Zhou, Mingfei – TE05 Walker, Nick – MH07, MH08, MI01 Schmid, Philipp C – WF04, WF05 WB05, RA03, FC01 Thurston, Glen K – ML05 Xue, Ci – WG08 Zhou, Zunwu – MH04 Wallentine, Spencer – WH05, WK06 Schmidt, Dag – MJ01 Steimle, Timothy – TE07, TE08, TE09 Tian, Zhong-Qun – TH05, RL10 Zhu, Boxing – TD01 Wang, Dandan – FC07 Schmitz, Joel R – WC10, WD01 Stephens, Ian – RG02 Tibbetts, Katharine Moore – TF02, Zhu, Xiaoyang – TK03 Wang, Hailing – TE07, TE09 Y Schneiker, Anita – ML06 Stephens, Susanna L. – TJ02, TJ03, TF03 Ziffer, Mark E – TK03 Wang, Honghao – MH04 Schnell, Melanie – TA03, TB08, TJ04, WI07 Titov, Anatoly – TE10 Zinga, Samuel – TA04, TA05 Wang, Jin – ML09 Yachmenev, Andrey – FA07, FF04 TC05, WB05, RA03, RH01, Stewart, Gabriel A. – WC04, RL09 Tiwari, P. K. – RL01, RL02, RL07 Zinn, Sabrina – WB05 Wang, Jue – TK03 Yamasaki, Sho – MJ04 RH02, RH05, RH07, FC01 Stewart, Jacob – ML03 Todd, Ethan – RG03 Ziurys, Lucy M. – WA01, WA03, Wang, Lee-Ping – WD04 Yan, Elsa – MA02 Schreier, Phillip – WF02 Stierwalt, David A. – MJ08 Tokaryk, Dennis W. – TI03, TI05, WJ07, WJ08 Wang, Lichang – MK07, MK09 Yan, Yi – FF05 Schreiner, Peter R. – RH05 Stitsky , Joseph – TJ06 RL08 Zobov, Nikolay F. – WD03 Ward, Meredith – FD05, FD06 Yang, Dong-Sheng – WF09, WJ10 Schroder,¨ Benjamin – FF01 Stollenwerk, Patrick R – TD09 Topfer,¨ Matthias – WF04 Zou, Luyao – FB04 Ward, Timothy B – TH09 Yang, Fan – MJ01 Schueler, Robert M – WL10 Stopkowicz, Stella – TI04 Topolski, Josey E – FF02 Zwier, Timothy S. – ML07, TH03, Wasserman, Joshua G – WH09 Yang, Haifeng – RG02 Schultz, Chase P – TA05 Strom, Aaron I. – TF08, TF09 Totleben, Lia – WH08 TJ08, TJ09, TJ10, TL02, WI02, Watanabe, Kyohei – TI06 Yang, Jie – FD03 Schwaab, Gerhard – FC02 Stuart, Devon J. – RH03 Trabelsi, Tarek – TH01 WI06 Schwan, Raffael – FC02 Su, Dianqiang – TE01 Tran, Minh Nhat – ML03 Scolati, Haley N. – WC02 Suas-David, Nicolas – TF05, TF06 Tremblay, Benoˆıt – WJ09 Scrape, Preston G. – ML02, TD05, Suhm, Martin A. – MH05 Tripathi,G.N.R.–TD08 FB07 Suits, Arthur – TF05, TF06 Tsuge, Masashi – WD07 Sears, Trevor – FE09 Sukhoviya, M.I. – WD06 Tsukiyama, Koichi – MG03, FA01 Sebald, Peter – FF01 Sun, Dewei – ML07, WI02 Tsunekawa, Shozo – TI07 Seifert, Nathan A. – MH09, WB03 Sun, Wenhao – TJ05, TJ06, FA04 Tsybizova, Alexandra – WB06 Sekutor, Marina – RH05 Sun, Yu Robert – ML09, TE03 Turut, Joan – MJ09, MJ10 Shafranyosh, I.I. – WD06 Sunahori, Fumie X – TD02 Twagirayezu, Sylvestre – TL03 Shafranyosh, M.I. – WD06 Sundararajan, Pavithraa – WD07 Tyree, Daniel J – WL09, WL10

     

ŽŽ ‘–”‹„—–‡†–ƒŽ•™‹ŽŽ„‡Š‡Ž†‹–Š‡Š‡‹•–”› ‘’Ž‡šȋƒ†‹‡†‹ƒ–‡Ž›ƒ†Œ‘‹‹‰„—‹Ž†‹‰•ȌǤŠ‡ ’Ž‡ƒ”›–ƒŽ•™‹ŽŽ„‡Š‡Ž†ƒ ”‘••–Š‡“—ƒ†ȋƒ„‘—–͸ͲͲ̵Ȍ‹ ‘‡ŽŽ‹‰‡”—†‹–‘”‹—Ǥ



1DWXUDO +LVWRU\ %XLOGLQJ

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dĂůŬƐ

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   ȋȌ

‘›‡•ƒ„‘”ƒ–‘”›Š‘—•‡•‘—”‡‰‹•–”ƒ–‹‘ƒ†šŠ‹„‹–‘”Ȁ‡ˆ”‡•Š‡–‘‘•ȋŠ‡‹•–”›‹„”ƒ”›Ȍǡ–Š‡ 1DWXUDO ‘’—–‡”ƒ„ȋͳͷͳȌǡƒ†–™‘Ž‡ –—”‡ŠƒŽŽ•ȋͳͲͲƒ†ʹͳ͹ȌǤ +LVWRU\ %XLOGLQJ



   ȋȌ     ȋȌ

Š‡‹•–”›‡š‹•‹‡†‹ƒ–‡Ž›–‘–Š‡•‘—–Š‘ˆ‘›‡•ƒ„‘”ƒ–‘”›ƒ ”‘••ƒ’‡†‡•–”‹ƒ™ƒŽ™ƒ›Ǥ –Šƒ• ‹•ƒ—Ž–‹Ǧ™‹‰„—‹Ž†‹‰Ž‘ ƒ–‡†ƒ ”‘••–Š‡•–”‡‡––‘–Š‡‡ƒ•–‘ˆ‘›‡•ƒ„‘”ƒ–‘”›ǤŠ‡Ž‡ –—”‡ŠƒŽŽ ‘‡Ž‡ –—”‡ŠƒŽŽȋͳͲʹͶȌ ȋͳͲʹȌ‹•‹–Š‡™‹‰ƒ ”‘••–Š‡’‡†‡•–”‹ƒ™ƒŽ™ƒ›–‘–Š‡‘”–Š‡ƒ•–‘ˆ‘‰‡”†ƒ•Ǥ

  ȋȌ

‘‰‡”†ƒ•ƒ„‘”ƒ–‘”›‹•ƒ ”‘••–Š‡•–”‡‡––‘–Š‡‡ƒ•–‘ˆŠ‡‹•–”›‡šǤ –Šƒ•‘‡Ž‡ –—”‡ŠƒŽŽȋ  ͳͳ͸ȌǤŽ‡ƒ•‡‘–‡–Šƒ–‹‘‰‡”†ƒ•ƒ„ǡ–Š‡‰”‘—†Ž‡˜‡Ž‹• ƒŽŽ‡†Dz ”‘—†dzƒ†–Š‡ ‹”•– Ž‘‘”‹• ‡“—‹˜ƒŽ‡––‘–Š‡‡ ‘† Ž‘‘”‹–Š‡‘–Š‡”„—‹Ž†‹‰•Ǥ     

ƒ–—”ƒŽ ‹•–‘”›—‹Ž†‹‰‹•‹‡†‹ƒ–‡Ž›‘”–Š‘ˆ‘›‡•ƒ„Ǥ –Šƒ•‘‡Ž‡ –—”‡ŠƒŽŽȋ ʹͲ͹ͻȌǤ







 ‘‡ŽŽ‹‰‡”—†‹–‘”‹—ȋŽ‡ƒ”›ƒ† –‡”‹••‹‘Ȍ   ȋͳͶȌ 

‘‡ŽŽ‹‰‡”—†‹–‘”‹—‹•Ž‘ ƒ–‡†ƒ––Š‡•‘—–Š‡†‘ˆ–Š‡—ƒ†ǤŠ‡ƒ‹†‘‘”•‘–Š‡‘”–Šȋ“—ƒ†Ȍ•‹†‡ ˆ›‘—’—” Šƒ•‡ƒ’ƒ”‹‰’‡”‹–ƒ†ƒ”‡•–ƒ›‹‰ƒ––Š‡†‘”ǡ›‘—™‹ŽŽ’ƒ”‹Ž‘–ͳͶȋƒ›•’‘–ȌǤͳͶ‹• ™‹ŽŽ‘’‡ƒ–ͺǣͳͲȋ–Š‡•‹†‡Ȁ™Š‡‡Ž Šƒ‹”†‘‘”™‹ŽŽ„‡‘’‡ƒ”‘—†ͺǣͲͲȌǤŠ‡”‡‹••‡ƒ–‹‰‘ ‡ƒ”Ž›†—‡•‘—–Š‘ˆ‘—•ˆ‹‡Ž† ƒŽŽ‘”Ǥ –Š‡ƒ‹Ž‡˜‡Žƒ†–Š‡—’’‡”„ƒŽ ‘›ǤŠ‡”‡‹•‘‡Ž‡˜ƒ–‘”‹–Š‡„—‹Ž†‹‰Ǥ  ƒ”‹‰‡ˆ‘” ‡‡–„‡‰‹•ƒ–͸ǣͲͲ‘‘†ƒ›ǡ•‘›‘—™‹ŽŽ‡‡†–‘Šƒ˜‡›‘—” ƒ”‹Ž‘–ͳͶ™‹–Š›‘—”  ’‡”‹–†‹•’Žƒ›‡†„‡ˆ‘”‡–Š‡ǤŠ‡”‡ƒ”‡ƒ›’ƒ”‹‰‡–‡”•‘Ǥ‡ƒ„‘†›”‹˜‡ȋƒ†‹–Š‡Ž‘–ƒ ”‘•• ˆ”‘‘—•ˆ‹‡Ž†Ȍ‹ˆ›‘—™‹•Š–‘’ƒ” Ž‘•‡”ˆ‘”•Š‘”–’‡”‹‘†•ȋʹͷ ‡–•Ȁͳͷ‹—–‡•Ȃ‰‡‡”ƒŽŽ›„‡–™‡‡͸ ƒ†͸ǡ„—– Š‡ –Š‡‡–‡”„‡ ƒ—•‡•‘‡‰‘—–‹ŽͻȌǤ  



      Ȁ –‘  ȋ™ƒŽ‹‰Ȍ  Ȁ –‘  ȋ„—•Ȍ

‘—•ˆ‹‡Ž†Ƭƒ••ƒŒƒ ƒŽŽ•ƒ”‡Œ—•–—†‡”ƒ‹Ž‡ȋͳͷǦʹͲ‹—–‡™ƒŽȌˆ”‘–Š‡ƒ‹•›’‘•‹—„—‹Ž†‹‰• Š‡”‡‹• ‘˜‡‹‡–ƒ†ˆ”‡‡„—••‡”˜‹ ‡„‡–™‡‡‘—•ˆ‹‡Ž†Ȁƒ••ƒŒƒ‘”•ƒ†ͳ„Ž‘ ˆ”‘–Š‡‡‡–‹‰ ˜‡—‡ǤŠ‡‡ŽŽ‘™‹‡’‹ •—’‘–Š‡ ‘”‡”‘ˆ ‹”•–ƒ†‡ƒ„‘†›ȋ‘—•ˆ‹‡Ž†Ȍǡƒ†ƒŽ•‘‘ ”‡‰‘”› ”‹˜‡ȋƒ••ƒŒƒȌ‹ˆ”‘–‘ˆ ‡„‡””›‘‘•ǡ†”‘’•‘ˆˆƒ––Š‡”ƒ‡”–‡–‡”ȋƒ ”‘••–Š‡•–”‡‡–ˆ”‘ ǦǤ‡–—”Ž‘ ƒ–‹‘•ƒ”‡–Š‡•ƒ‡„—–ƒ ”‘••–Š‡•–”‡‡–ǤŠ‡‡ŽŽ‘™‹‡™‹ŽŽƒŽ•‘–ƒ‡›‘—–‘ †‘™–‘™Šƒ’ƒ‹‰ǡ„—–›‘—™‹ŽŽ‡‡†–‘’ƒ›ˆ‘”›‘—””‡–—”ȋ‘Ž›‹–‘’•ƒ”‡ˆ”‡‡ȌǤ’’”‘š‹ƒ–‡Ž› ‡˜‡”›ͳͲ‹—–‡•†—”‹‰–Š‡†ƒ›Ǥ

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  Š‡ ‘Ž†‹‡’‹ •—’‘–Š‡ ‘”‡”‘ˆ ‹”•–ƒ†‡ƒ„‘†›ǡƒ†ƒŽ•‘‘ ”‡‰‘”›”‹˜‡‹ˆ”‘–‘ˆ ‡„‡””›  ‘‘•ƒ††”‘’•‘ˆˆƒ––Š‡”ƒ‡”–‡–‡”ȋƒ ”‘••–Š‡•–”‡‡–ˆ”‘ǦȌǤ‡–—”Ž‘ ƒ–‹‘•ƒ”‡ ƒ ”‘••–Š‡•–”‡‡–Ǥ—•‡˜‡”›̱ͳͲ‹—–‡•†—”‹‰–Š‡†ƒ›ȋ‘ˆˆ•‡–ˆ”‘–Š‡‡ŽŽ‘™‹‡„›ͷ‹—–‡•ȌǤ 

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