DOCSLIB.ORG

Structural Features of the Carbon-Sulfur Chemical Bond: a Semi-Experimental Perspective Supporting Information

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
Structural Features of the Carbon-Sulfur Chemical Bond: a Semi-Experimental Perspective Supporting Information Structural features of the carbon-sulfur chemical bond: a semi-experimental perspective Supporting Information Emanuele Penocchio, Marco Mendolicchio, Nicola Tasinato, and Vincenzo Barone∗ Scuola Normale Superiore, Pisa, Italy E-mail: [email protected] ∗To whom correspondence should be addressed 1 In Table 1 we focus on molecules reported in Table 2 of the main article and compare reference SE equilibrium parameters with ab-initio predictions obtained with B3LYP/SNSD, B2PLYP/VTZ, M06-2X, and BHandH model chemistries. β In Table 2, experimental rotational constants, ∆Bvib calculated at B3LYP/SNSD and B2PLYP/VTZ β levels of theory, and ∆Bel calculated at B3LYP/AVTZ level are reported for all the species discussed in the main text. Table 1: Comparison between reference SE equilibrium parameters and ab-initio ones ob- tained using functionals with a different amount of Hartree-Fock exchange (see main text). Distances in A,˚ angles in degrees. Atom numbering as in Figure 2 of the main work. SEa re re B3LYP/SNSD B2PLYP/VTZ M06-2X/VTZ BHandH/VTZ SE { Sulfur chains { isothiocyanic acid r(S-C) 1:5832 1:5744 1:5713 1:5588 1:5678(7) r(C-N) 1:2091 1:2047 1:1922 1:179 1:2047(9) r(N-H) 1:0102 1:0035 1:0035 0:9974 1:0070(9) a(S-C-N) 173:77 173:95 174:81 175:42 172:23(18) a(H-N-C) 129:67 131:50 134:72 137:28 129:75(5) thioformaldehyde r(S-C) 1:6227 1:6135 1:60089 1:58782 1:6093(1) r(C-H) 1:0918 1:0859 1:08702 1:0849 1:0854(2) a(H-C-S) 121:95 122:01 122:025 121:964 121:73(2) thioketene r(S-C) 1:5724 1:5623 1:5546 1:5426 1:5556(4) r(C-C) 1:3107 1:3082 1:3021 1:2899 1:3107(5) r(C-H) 1:0863 1:0801 1:0811 1:0793 1:0806(1) a(C-C-H) 120:66 120:46 120:31 129:34 120:15(1) propadienethione r(S1-C2) 1:5876 1:5776 1:5673 1:5546 1:5715(15) r(C2-C3) 1:2722 1:2691 1:2679 1:2571 1:2702(18) r(C3-C4) 1:3223 1:3191 1:3119 1:3003 1:3228(9) r(C4-H) 1:0905 1:0848 1:0851 1:0832 1:0842(3) a(H-C4-C3) 121:80 121:68 121:48 121:49 121:20(2) 2 β β Table 2: Experimental rotational constants, ∆Bvib, and ∆Bel are reported for all the species discussed in the main text. All data are in MHz, see main text for atom numbering. β EXP β β (B0 ) −∆Bvib ∆Bel B3LYP/SNSD B2PLYP/VTZ B3LYP/AVTZ thiirane parent A 21973:6349a 200:215 211:715 −0:196 B 10824:8925a 65:624 68:231 −0:153 C 8026:24744a 65:267 68:182 0:212 33S A 21973:4850b 200:338 211:838 −0:196 B 10683:8236b 64:437 67:002 −0:148 C 7948:33140b 64:331 67:208 0:208 34S A 21973:3890b 200:467 211:955 −0:196 B 10551:1131b 63:331 65:852 −0:143 C 7874:59486b 63:451 66:291 0:205 13C A 21482:4120b 192:968 204:216 −0:187 B 10653:3545b 63:839 66:401 −0:150 C 7866:25519b 63:373 66:234 0:202 4D A 15471:0c 125:390 130:939 −0:096 B 9197:6c 53:388 54:908 −0:116 C 6819:0c 50:661 52:345 0:150 thiazole parent A 8529:403d 65:070 66:728 −0:509 B 5505:746d 31:412 32:566 −0:261 C 3344:291d 23:458 24:190 0:074 34S A 8529:220d 64:950 66:612 −0:509 B 5353:320d 30:318 31:417 −0:247 C 3287:440d 22:898 23:610 0:071 15N A 8471:550d 64:081 65:736 −0:498 B 5401:340d 30:682 31:870 −0:253 C 3296:756d 22:959 23:701 0:072 13 d C2 A 8335:696 63:323 64:956 −0:485 B 5504:919d 31:037 32:201 −0:262 C 3313:801d 23:103 23:834 0:072 13 d C4 A 8460:999 64:179 65:865 −0:505 B 5412:722d 30:737 31:817 −0:251 C 3299:390d 23:007 23:714 0:072 13 d C5 A 8317:847 62:972 64:590 −0:484 B 5505:989d 31:185 32:327 −0:261 C 3311:352d 23:108 23:828 0:072 d D2 A 7867:590 57:225 58:656 −0:433 B 5505:486d 31:441 32:560 −0:261 C 3237:439d 22:304 22:982 0:069 d D4 A 8325:228 63:225 64:838 −0:499 B 5229:035d 29:128 30:122 −0:230 C 3210:280d 22:063 22:727 0:068 d D5 A 7855:939 56:097 57:527 −0:429 B 5498:517d 31:716 32:895 −0:263 C 3233:047d 22:211 22:910 0:069 References: a) 1; b) 2; c) 3; d) 4; 3 | Table 2 continued | β EXP β β (B0 ) −∆Bvib ∆Bel B3LYP/SNSD B2PLYP/VTZ B3LYP/AVTZ 1,2,3-thiadiazole parent A 8711:38a 65:265 67:814 −0:840 B 5847:09a 43:587 46:446 −0:319 C 3496:59a 28:651 30:087 0:072 34S A 8711:41a 65:140 67:628 −0:841 B 5686:12a 42:073 44:872 −0:301 C 3438:37a 28:016 29:431 0:070 15 a N2 A 8502:61 63:456 65:949 −0:797 B 5846:91a 43:211 45:961 −0:319 C 3462:38a 28:199 29:580 0:071 15 a N3 A 8650:57 63:832 66:238 −0:821 B 5740:43a 42:986 45:770 −0:310 C 3448:54a 28:150 29:538 0:070 13 a C4 A 8641:88 65:077 67:632 −0:836 B 5742:95a 42:139 44:936 −0:304 C 3448:07a 28:040 29:460 0:070 13 a C5 A 8486:04 62:670 65:041 −0:799 B 5847:30a 43:416 46:235 −0:319 C 3459:77a 28:139 29:522 0:070 a D4 A 8518:49 65:578 68:230 −0:826 B 5530:15a 39:050 41:553 −0:276 C 3351:31a 26:793 28:134 0:066 a D5 A 7998:72 55:213 57:234 −0:704 B 5839:27a 44:759 47:498 −0:321 C 3373:24a 27:162 28:422 0:067 34 a S, D5 A 7997:22 55:168 57:183 −0:705 B 5680:08a 43:149 45:841 −0:303 C 3319:24a 26:586 27:841 0:065 15 a N2,D5 A 7815:75 53:726 55:746 −0:668 B 5838:42a 44:426 47:025 −0:322 C 3339:97a 26:728 27:935 0:066 15 a N3,D5 A 7949:74 53:942 55:844 −0:687 B 5728:83a 44:165 46:728 −0:313 C 3327:53a 26:706 27:888 0:065 13 a C4,D5 A 7939:11 55:271 57:341 −0:703 B 5737:70a 43:209 45:904 −0:306 C 3328:66a 26:605 27:868 0:065 13 a C5,D5 A 7816:59 53:038 55:006 −0:673 B 5839:34a 44:644 47:317 −0:322 C 3340:43a 26:678 27:896 0:065 2D A 7831:12a 56:160 58:338 −0:698 B 5528:41a 39:932 42:295 −0:277 C 3238:85a 25:479 26:665 0:061 References: a) 5. 4 | Table 2 continued | β EXP β β (B0 ) −∆Bvib ∆Bel B3LYP/SNSD B2PLYP/VTZ B3LYP/AVTZ 1,3,4-thiadiazole parent A 8907:376a 72:606 74:365 −0:599 B 5569:321a 30:842 32:573 −0:336 C 3424:779a 24:590 25:555 0:061 34S A 8907:484a 72:442 74:265 −0:599 B 5408:526a 29:745 31:414 −0:317 C 3363:296a 23:962 24:916 0:058 15N A 8838:554a 71:489 73:271 −0:590 B 5469:994a 30:167 31:892 −0:323 C 3376:938a 24:078 25:044 0:059 13C A 8696:617a 70:552 72:217 −0:571 B 5569:263a 30:531 32:225 −0:335 C 3393:119a 24:248 25:179 0:060 2D A 7565:918a 55:432 56:874 −0:431 B 5567:338a 31:016 32:603 −0:335 C 3205:561a 22:161 22:991 0:053 34S, 2D A 7566:044a 55:306 56:759 −0:431 B 5407:324a 29:911 31:424 −0:318 C 3151:862a 21:641 22:451 0:051 15N, 2D A 7517:216a 54:713 56:151 −0:426 B 5467:128a 30:307 31:898 −0:323 C 3163:478a 21:724 22:555 0:052 13C, 2D A 7413:475a 53:955 55:397 −0:414 B 5567:237a 30:730 32:273 −0:335 C 3177:816a 21:835 22:647 0:052 D A 8190:071a 63:117 64:734 −0:506 B 5568:156a 30:962 32:572 −0:336 C 3312:800a 23:347 24:229 0:057 34S, D A 8189:876a 62:992 64:610 −0:506 B 5407:830a 29:860 31:407 −0:317 C 3255:322a 22:779 23:641 0:054 15N-D A 8134:555a 62:364 63:965 −0:499 B 5469:463a 30:244 31:825 −0:323 C 3268:673a 22:887 23:756 0:056 15N, D A 8130:079a 62:123 63:748 −0:499 B 5467:331a 30:293 31:883 −0:323 C 3267:174a 22:867 23:743 0:056 13C-D A 8019:104a 61:382 62:935 −0:485 B 5568:179a 30:648 32:244 −0:335 C 3284:460a 23:004 23:866 0:056 13C, D A 8004:030a 61:433 62:992 −0:483 B 5567:949a 30:642 32:245 −0:335 C 3281:849a 23:013 23:879 0:056 References: a) 6.
Load more

Recommended publications
  • A Comprehensive Investigation on the Formation of Organo-Sulfur Molecules in Dark Clouds Via Neutral-Neutral Reactions
    A&A 395, 1031–1044 (2002) Astronomy DOI: 10.1051/0004-6361:20021328 & c ESO 2002 Astrophysics A comprehensive investigation on the formation of organo-sulfur molecules in dark clouds via neutral-neutral reactions M. Yamada1, Y. Osamura1, and R. I. Kaiser2;? 1 Department of Chemistry, Rikkyo University, 3-34-1 Nishi-ikebukuro, Tokyo 171-8501, Japan 2 Department of Chemistry, University of York, YO10 5DD, UK Received 11 June 2002 / Accepted 9 September 2002 Abstract. Fifteen reactions on the doublet HCnS and singlet/triplet H2CnS(n = 1; 2) potential energy surfaces have been investi- gated theoretically via electronic structure calculations to unravel the formation of hydrogen deficient, sulfur bearing molecules via bimolecular reactions of two neutral species in cold molecular clouds. Various barrierless reaction pathways to synthe- size astronomically observed CnS and hitherto undetected HCnS(n = 1; 2) isomers are offered. These data present important 2 2 guidance to search for rotational transitions of the elusive thioformyl HCS(X A0) and thioketenyl HCCS(X Π) radicals in the interstellar medium. Key words. astrochemistry – ISM: molecules – molecular processes – methods: miscellaneous 1. Introduction terminated counterparts HCnSandCnSH have not been de- tected in the interstellar medium yet. However, these molecules Untangling the synthetic routes to form sulfur-carrying might represent the missing source of molecular-bound sul- molecules in the interstellar medium is a significant instru- fur in the interstellar medium. Hydrogen deficient organosul- ment to understand the chemical evolution and physical con- 2 2 fur molecules like HCS(X A0) and HCCS(X Π) resemble also ditions in star forming regions and in circumstellar envelopes important reaction intermediates which could lead to sulfur (Minh & van Dishoeck 2000).
    [Show full text]
  • H2CS) and Its Thiohydroxycarbene Isomer (HCSH
    A chemical dynamics study on the gas phase formation of thioformaldehyde (H2CS) and its thiohydroxycarbene isomer (HCSH) Srinivas Doddipatlaa, Chao Hea, Ralf I. Kaisera,1, Yuheng Luoa, Rui Suna,1, Galiya R. Galimovab, Alexander M. Mebelb,1, and Tom J. Millarc,1 aDepartment of Chemistry, University of Hawai’iatManoa, Honolulu, HI 96822; bDepartment of Chemistry and Biochemistry, Florida International University, Miami, FL 33199; and cSchool of Mathematics and Physics, Queen’s University Belfast, Belfast BT7 1NN, Northern Ireland, United Kingdom Edited by Stephen J. Benkovic, The Pennsylvania State University, University Park, PA, and approved August 4, 2020 (received for review March 13, 2020) Complex organosulfur molecules are ubiquitous in interstellar molecular sulfur dioxide (SO2) (21) and sulfur (S8) (22). The second phase clouds, but their fundamental formation mechanisms have remained commences with the formation of the central protostars. Tempera- largely elusive. These processes are of critical importance in initiating a tures increase up to 300 K, and sublimation of the (sulfur-bearing) series of elementary chemical reactions, leading eventually to organo- molecules from the grains takes over (20). The subsequent gas-phase sulfur molecules—among them potential precursors to iron-sulfide chemistry exploits complex reaction networks of ion–molecule and grains and to astrobiologically important molecules, such as the amino neutral–neutral reactions (17) with models postulating that the very acid cysteine. Here, we reveal through laboratory experiments, first sulfur–carbon bonds are formed via reactions involving methyl electronic-structure theory, quasi-classical trajectory studies, and astro- radicals (CH3)andcarbene(CH2) with atomic sulfur (S) leading to chemical modeling that the organosulfur chemistry can be initiated in carbonyl monosulfide and thioformaldehyde, respectively (18).
    [Show full text]
  • UV-Spectrum of Thioformaldehyde-S-Oxide
    Electronic Supplementary Material (ESI) for Chemical Communications This journal is © The Royal Society of Chemistry 2013 Matrix Isolation and Spectroscopic Properties • of the Methylsulfinyl Radical CH3(O)S [a] [b] [b] Hans Peter Reisenauer,* Jaroslaw Romanski, Grzegorz Mloston,* Peter R. Schreiner[a] [a] Justus-Liebig University, Institute of Organic Chemistry, Heinrich-Buff-Ring 58, D-35392 Giessen, Fax: (+49) 641-99-34209; E-mail: [email protected] [b] University of Lodz, Section of Heteroorganic Compounds, Tamka 12, PL-91-403 Lodz, Fax: (+48) (42) 665 51 62; E-mail: [email protected] Supplementary Information Table S1. Experimental (Ar, 10 K) and computed (AE-CCSD(T)/cc-pVTZ, harmonic approximation, no scaling) the IR spectra of 3. 13 3 C-3 D3-3 a b a b a b Sym. Approx. Band Position (Intensity) Band Position (Intensity) Band Position (Intensity) Mode Computation Experiment Computation Experiment Computation Experiment a’’ CH str. 3151.3 (2.1) 2995.4 3139.3 (2.1) n.o. 2336.4 (1.2) 2247.2 a’ CH str. 3149.3 (4.1) (vw) 3137.5 (4.0) n.o. 2334.5 (2.2) (vw) 2919.4 2095.5 a’ CH str. 3065.6 (4.3) 3062.7 (4.5) n.o. 2194.2 (1.4) (vw) (vw) CH 1062.8 a’ 3 1477.4 (6.5) 1417.1 (w) 1474.8 (6.6) 1414.6 (w) 1028.7 (s) def. (17.3) CH a’’ 3 1464.4 (7.8) 1405.2 (w) 1461.7 (7.8) 1401.4 (w) 1058.5 (3.7) 1025.6 (w) def.
    [Show full text]
  • Thermal Averaging of the Indirect Nuclear Spin-Spin Coupling Constants of Ammonia: the Importance of the Large Amplitude Inversion Mode Andrey Yachmenev, Sergei N
    Thermal averaging of the indirect nuclear spin-spin coupling constants of ammonia: The importance of the large amplitude inversion mode Andrey Yachmenev, Sergei N. Yurchenko, Ivana Paidarová, Per Jensen, Walter Thiel, and Stephan P. A. Sauer Citation: J. Chem. Phys. 132, 114305 (2010); doi: 10.1063/1.3359850 View online: https://doi.org/10.1063/1.3359850 View Table of Contents: http://aip.scitation.org/toc/jcp/132/11 Published by the American Institute of Physics Articles you may be interested in Accurate ab initio vibrational energies of methyl chloride The Journal of Chemical Physics 142, 244306 (2015); 10.1063/1.4922890 Automatic differentiation method for numerical construction of the rotational-vibrational Hamiltonian as a power series in the curvilinear internal coordinates using the Eckart frame The Journal of Chemical Physics 143, 014105 (2015); 10.1063/1.4923039 Theoretical rotation-vibration spectrum of thioformaldehyde The Journal of Chemical Physics 139, 204308 (2013); 10.1063/1.4832322 High-level ab initio potential energy surfaces and vibrational energies of H2CS The Journal of Chemical Physics 135, 074302 (2011); 10.1063/1.3624570 A highly accurate ab initio potential energy surface for methane The Journal of Chemical Physics 145, 104305 (2016); 10.1063/1.4962261 Ro-vibrational averaging of the isotropic hyperfine coupling constant for the methyl radical The Journal of Chemical Physics 143, 244306 (2015); 10.1063/1.4938253 THE JOURNAL OF CHEMICAL PHYSICS 132, 114305 ͑2010͒ Thermal averaging of the indirect nuclear spin-spin coupling constants of ammonia: The importance of the large amplitude inversion mode Andrey Yachmenev,1 Sergei N.
    [Show full text]
  • Version 038 – Exam 2 – Mccord – (53130) 1 This Print-Out Should
    Version038–Exam2–McCord–(53130) 1 This print-out should have 31 questions. 3. sp3 Multiple-choice questions may continue on the next column or page – find all choices 4. Pure pz orbitals are used in bonding. before answering. 5. sp3d McCord CH301tt Explanation: The structure is b b b This exam is only for b O McCord’s Tues/Thur CH301 class. C If Quest works properly, you should be able H3C CH3 to see your score for this exam by 11:30 PM tonight. Do realize however that Quest has 003 10.0 points been taking up to 8 hours to get through the Which of the molecules b b b grading, so your score might appear bit by bit. b O I will post an announcement on our web page I) and/or Quest when I feel like all bubblesheets H H have been graded. b b b b b b Cl PLEASE carefully bubble in your UTEID and Version Number! We av- II) b b B b b b erage about 20-30 students per exam that b b b b Cl Clb b misbubble this information. Get it right! b b b b b b b b III) b Cl Cl b b b b 001 10.0 points contains polar covalent bonds but is NOT Choose the species that is incorrectly matched itself a polar molecule? with electronic geometry about the central atom. 1. III only 1. CF4 : tetrahedral 2. II and III only 2. BeBr2 : linear 3. I and II only 3. H2O : tetrahedral 4.
    [Show full text]
  • Anchoring the Potential Energy Surfaces of Homogenous and Heterogenous Dimers of Formaldehyde and Thiofomaldehyde
    ANCHORING THE POTENTIAL ENERGY SURFACES OF HOMOGENOUS AND HETEROGENOUS DIMERS OF FORMALDEHYDE AND THIOFOMALDEHYDE by Christina Michelle Holy A thesis submitted to the faculty of The University of Mississippi in partial fulfillment of the requirements of the Sally McDonnell Barksdale Honors College Oxford May 2014 Approved by _____________________________________ Advisor: Professor Gregory Tschumper _____________________________________ Reader: Associate Professor Nathan Hammer _____________________________________ Reader: Professor Susan Pedigo © 2014 Christina Michelle Holy ALL RIGHTS RESERVED ii ACKNOWLEDGEMENTS Many people in the Department of Chemistry and Biochemistry here at the University of Mississippi were of great assistance during the work presented in this manuscript. I would like to thank the Mississippi Center for Supercomputing Research for the use of their computational facilities and the research group of Dr. Gregory Tschumper for their guidance and computational assistance. Specifically, I would like to thank Eric Van Dornshuld for his continual support and advisement throughout this research project. Lastly, I would like to thank my advisor, Dr. Gregory Tschumper, for allowing me to work in his laboratory as well as providing me with a worthwhile project to fulfill this thesis requirement. iii ABSTRACT This work characterizes five stationary points of the formaldehyde dimer, (CH2O)2, two of which are minima, seven newly-identified stationary points of the formaldehyde/thioformaldehyde (mixed) dimer, CH2O/CH2S, four of which are minima, and five newly-identified stationary points of the thioformaldehyde dimer, (CH2S)2 , three of which are minima. Full geometry optimizations and corresponding harmonic vibrational frequencies were performed on CH2O and CH2S as well as each of the dimer configurations (Figures 3-5).
    [Show full text]
  • TA-02 Ion Science PID Response Factors USA V1.6.Pdf 1.43 MB
    Technical/Application Article 02 Version 1.6 19 July 2016 WRH/FD Ion Science PID Response Factors PID Response Photoionization Detectors (PIDs) respond to a broad range of organic and a few inorganic gaseous and volatile chemicals (‘volatiles’). In order for PID to respond to a volatile, the photon energy of the lamp must be greater than its ionization energy. Ion Science PIDs are available with 10.0 eV, 10.6 eV, and 11.7 eV lamps. This Technical Article lists the response factors (‘RF’s’) for over 800 volatiles with PID engaging these lamps. The RF relates the sensitivity of PID to a volatile to the sensitivity to the standard calibration gas isobutylene. The higher the RF, the lower the sensitivity. In the table ‘ZR’ means there is no response, NA that the value has not been measured (Not Available), and NV means that the compound is not volatile enough to measure accurately. For chemicals not listed, contact Ion Science for more information. Isobutylene as Reference Gas It is always most accurate to calibrate a PID directly with the compound to be measured. However, standard gas cylinders of many chemicals are not readily available, and in such cases isobutylene is the standard reference gas used to calibrate. The response of these chemicals differs to isobutylene by the factors listed in the table below. This table allows measurement of all the listed volatiles using only isobutylene for calibration. To obtain the true concentration of the target volatile chemical, multiply the apparent reading by the response factor listed in the table: True Concentration = Apparent Response x Response Factor For example, anisole has a response factor (RF) of 0.47 with a 10.6 eV lamp.
    [Show full text]
  • Criegee Intermediate-Hydrogen Sulfide Chemistry at the Air/Water
    Chemical Science View Article Online EDGE ARTICLE View Journal | View Issue Criegee intermediate-hydrogen sulfide chemistry at the air/water interface† Cite this: Chem. Sci.,2017,8,5385 Manoj Kumar,‡a Jie Zhong,‡a Joseph S. Francisco*a and Xiao C. Zeng*ab We carry out Born–Oppenheimer molecular dynamic simulations to show that the reaction between the smallest Criegee intermediate, CH2OO, and hydrogen sulfide (H2S) at the air/water interface can be observed within few picoseconds. The reaction follows both concerted and stepwise mechanisms with former being the dominant reaction pathway. The concerted reaction proceeds with or without the Received 22nd April 2017 involvement of one or two nearby water molecules. An important implication of the simulation results is Accepted 9th May 2017 that the Criegee-H2S reaction can provide a novel non-photochemical pathway for the formation of DOI: 10.1039/c7sc01797a aC–S linkage in clouds and could be a new oxidation pathway for H2S in terrestrial, geothermal and rsc.li/chemical-science volcanic regions. Creative Commons Attribution 3.0 Unported Licence. Carbon–sulfur linkages are ubiquitous in atmospheric, combus- hydrogen sulde (H2S) under water or acid catalysis could account tion, and biological chemistries. Thioaldehydes comprise an for the atmospheric formation of thioaldehydes and provide useful important class of carbon–sulfur compounds that has a broad guidelines for efficiently synthesizing thioaldehydes within labo- chemical appeal. For example, thioformaldehyde (HCHS) has been ratory environment.7,9
    [Show full text]
  • Submillimeter-Wave Spectroscopy of and Interstellar Search for Thioacetaldehyde
    Submillimeter-wave spectroscopy of and interstellar search for thioacetaldehyde L. Margul`esa, V. V. Ilyushinb,c,∗, B. A. McGuired, A. Bellochee, R. A. Motiyenkoa, A. Remijand, E. A. Alekseevb,c, O. Dorovskayab, J.-C. Guilleminf aUniv. Lille, CNRS, UMR 8523 - PhLAM - Physique des Lasers Atomes et Mol´ecules,F-59000 Lille, France bInstitute of Radio Astronomy of NASU, 4, Mystetstv St., Kharkiv, 61002, Ukraine cQuantum Radiophysics Department, V.N. Karazin Kharkiv National University, Svobody Square 4, 61022, Kharkiv, Ukraine dNational Radio Astronomy Observatory, Charlottesville, VA 22903, USA eMax-Planck-Institut f¨urRadioastronomie, Auf dem H¨ugel69, 53121 Bonn, Germany fUniv. Rennes, Ecole Nationale Sup´erieure de Chimie de Rennes, CNRS, ISCR { UMR 6226, F-35000 Rennes, France Abstract We present a new study of the millimeter and submillimeter wave spectra of the thioacetaldehyde molecule, CH3CHS, a sulfur-bearing analog of the ubiquitous interstellar molecule acetaldehyde (CH3CHO). Here, we present a laboratory investigation aimed at determining accurate spectroscopic parameters for CH3CHS to enable astronomical searches for this molecule using radio telescope arrays at millimeter and submillimeter wavelengths. New laboratory measurements have been carried out between 150 and 660 GHz using the spectrometer of PhLAM in Lille (France). Rotational transitions up to J = 60 were assigned in the ground, first and second excited torsional states of thioacetaldehyde and fit using the RAM Hamiltonian model. The final fit includes 62 parameters to give an overall weighted root-mean-square deviation of 0.9. On the basis of our spectroscopic results, CH3CHS was searched for, but not detected, in data from the Atacama Large Millimeter/submillimeter Array (ALMA) between 84 GHz and 114 GHz toward the hot molecular core Sgr B2(N2).
    [Show full text]
  • OLCT200 PID Application Note
    OLCT200 PID Application note PID Response Factor PID Response Photoionization Detectors (PIDs) respond to a broad variety of organic gases and vapors, and some inorganic compounds. In order to get a response, the photon energy of the lamp must be greater than the ionization energy of the compound. PIDs are available with 10.6 eV lamps. This Technical Article lists the response factors for over 800 compounds with these lamps. The factors presented are inverse to the response, i.e., the higher the number the lower the response. In the table ‘ZR’ means there is no response, NA that the value has not been measured (Not Available), and NV means that the compound is not volatile enough to measure accurately even if its ionization energy is low enough. Isobutylene as Reference Gas It is always most accurate to calibrate a PID directly with the compound to be measured. However, standard gas cylinders of many chemicals are not readily available, and in such cases isobutylene is the standard reference gas used to calibrate. The response of these chemicals differs to isobutylene by the factors listed in the table below. This table allows measurement of any of the compounds in it using only isobutylene for calibration. To obtain the true concentration of the target chemical, multiply the apparent reading by the response factor listed in the table: True Concentration = Apparent Response x Response Factor For example, anisole has a response factor (RF) of 0.47 with a 10.6 eV lamp. Therefore, a reading of 10 ppm using an isobutylene-calibrated unit would correspond to: True Concentration = 10 ppm x 0.47 = 4.7 ppm Most of the Response Factors are pre-programmed into a compound library and can be called up to make the PID read out in units of the compound of interest.
    [Show full text]
  • Electron Induced Chemistry of Thioformaldehyde
    RSC Advances Electron induced chemistry of Thioformaldehyde Journal: RSC Advances Manuscript ID RA-ART-09-2015-019662.R1 Article Type: Paper Date Submitted by the Author: 11-Nov-2015 Complete List of Authors: Limbachiya, Chetan; The M. S. University Baroda, Vadodara - 390001, Department of applied Physics CHAUDHARI, ASHOK; Government Engineering College Patan,, PHYSICS DESAI, HARDIK; DEPARTMENT OF PHYSICS, SARDAR PATEL UNIVERSITY, VALLABH VIDYANAGAR, PHYSICS VINODKUMAR, MINAXI; V.P & R.P.T.P. SCIENCE COLLEGE, ELECTRONICS; P.G. DEPARTMENT OF PHYSICS, SARDAR PATEL UNIVERSITY, PHYSICS Subject area & keyword: Biophysics - Physical < Physical Page 1 of 15 RSC Advances Electron induced chemistry of Thioformaldehyde Chetan Limbachiyaa,Ashok Chaudharib, Hardik Desaic and Minaxi Vinodkumar∗d Received Xth XXXXXXXXXX 20XX, Accepted Xth XXXXXXXXX 20XX First published on the web Xth XXXXXXXXXX 200X DOI: 10.1039/b000000x A comprehensive theoretical study is carried out for electron interactions with thioformaldehyde (H2CS) over a wide range of impact energies (0.01 eV to 5000 eV). Owing to wide energy range we have been able to compute target properties and investigate variety of processes and report data on resonances, vertical electronic excitation energies, differential cross sections (DCS), momentum transfer cross sections (MTCS), total ionization cross sections (TICS) and total cross sections (TCS) as well as scattering rate coefficients. Due to complexity involved in scattering calculations, two different theoretical formalisms are used. We have employed ab initio R-matrix method (0.01 eV to ∼ 20 eV) and the spherical complex optical potential (SCOP) method (∼20 eV to 5000 eV) to compute the cross sections. The R-matrix calculations are performed using close coupling approximation employing static exchange plus polarization (SEP) model with the aid of basis sets, 6-31G* (14 target states) and cc-pVTZ (16 target states).
    [Show full text]
  • A Study of the Charge Distribution in Unconjugated Thiocarbonyl Compounds: a Comparison with Carbonyl and Imine Chromophores
    South Dakota State University Open PRAIRIE: Open Public Research Access Institutional Repository and Information Exchange Electronic Theses and Dissertations 1974 A Study of the Charge Distribution in Unconjugated Thiocarbonyl Compounds: a Comparison with Carbonyl and Imine Chromophores John Yuchu Lee Follow this and additional works at: https://openprairie.sdstate.edu/etd Recommended Citation Lee, John Yuchu, "A Study of the Charge Distribution in Unconjugated Thiocarbonyl Compounds: a Comparison with Carbonyl and Imine Chromophores" (1974). Electronic Theses and Dissertations. 4734. https://openprairie.sdstate.edu/etd/4734 This Thesis - Open Access is brought to you for free and open access by Open PRAIRIE: Open Public Research Access Institutional Repository and Information Exchange. It has been accepted for inclusion in Electronic Theses and Dissertations by an authorized administrator of Open PRAIRIE: Open Public Research Access Institutional Repository and Information Exchange. For more information, please contact [email protected]. STUDY CB1'RGE DISTRIBUTION UNCONJUGATED A OF THE Id THIOCARI30NYL COMPOUNDS: COMPARISON A WITH THE CARBONYL AND IMINE CHRO!-DPHORES . BY JOHN LEE YUCHU �.UTH _DAKOTA STATE UNIVERSITY LIBRARY thesis A su:C:-:iitted fulfill::1ent of the the in partial requirer,ents for degree in Master of Cheriistry, Science, ��jor South Dakota State Unive1·sity 1974 '1, I A STUDY OF THE CHARGE DISTRIBUTION IN UNCONJUGATED THIOCARBONYL COMPOUNDS: A COMPARISON WITH THE CARBONYL AND IMINE CHROr-OPHORES Abstract JOHN YUCHU LEE Under the supervision of Dr . James Worman Via a literature search it has been shown, by means of the ira spectra of thioamides, the dipole moments of thiocarbonyl compounds , the basicity of thioamides and thioureas, the acidity of carboxylic acids carrying a substituent with the thiocarbonyl function, LCAO-b method, and proton· chemical shifts, that the thiocarbonyl group me has tendency to give a greater mesomeric interaction than the (�) carbonyla group (£) with electron donating heteroatoms.
    [Show full text]