Investigation of Prebiotic Molecules Using O(1D) Insertion Reactions

Brian Hays, Jake Laas, Bridget Alligood DePrince, Jay Kroll and Susanna Widicus Weaver

Emory University Complex Chemistry in the ISM

H2O + hn OH + H H2 + O hn

CH3OH + hn CH3 + OH CH3O + H CH2OH + H

H2O, CO, CH3OH, NH3 + hn NH2 + H NH3 , H2CO Ice mantle

Charnley, 2001 Garrod, Widicus Weaver, & Herbst, 2008 Complex Chemistry in the ISM

H2O + hn OH + H H2 + O hn

CH3OH + hn CH3 + OH CH3O + H CH2OH + H

H2O, CO, CH3OH, NH3 + hn NH2 + H NH3 , H2CO Ice mantle

CH2OH + OH CH2(OH)2 Methanediol CH2OH + CH3O CH3OCH2OH Methoxymethanol

CH2OH + NH2 HOCH2NH2 Aminomethanol

Charnley, 2001 Garrod, Widicus Weaver, & Herbst, 2008 Complex Chemistry in the ISM

H2O + hn OH + H H2 + O hn

CH3OH + hn CH3 + OH CH3O + H CH2OH + H

H2O, CO, CH3OH, NH3 + hn NH2 + H NH3 , H2CO Ice mantle

CH2OH + OH CH2(OH)2 Methanediol CH2OH + CH3O CH3OCH2OH Methoxymethanol

CH2OH + NH2 HOCH2NH2 Aminomethanol

CH3OH2+ HCOOH

or H3+ -H2O

aminomethanol protonated glycine aminomethanol Charnley, 2001 Garrod, Widicus Weaver, & Herbst, 2008 Proposed Formation Route for Laboratory Spectroscopy

•Molecules unstable under terrestrial conditions so no laboratory spectra exist 1.968 eV energy •Produce these 1 molecules using O( D) barrierless O(1D) E 3 insertion reactions O( P)

•O(1D) primarily inserts into bonds that are H-X where X=C, N, O, H Aminomethanol Formation CCSD(T)//MP2/aug-cc-pVTZ

Hays and Widicus Weaver, in revision Aminomethanol Spectrum

Amine wag ~2140 cm-1

Hydroxyl wag ~684 cm-1

Constant Aminomethanol A (GHz) 38.6930 B (GHz) 9.5457 C (GHz) 8.5868

μA (Debye) -0.377

μB (Debye) -0.995

μC (Debye) 1.341 MP2/aug-cc-pVTZ Hays and Widicus Weaver, in revision O(1D) Insertion into Methane

• O3 + hν(248 nm)  1 1 O2( Δ) + O( D) ~90% 3 3 O2( Σ) + O( P) ~10%

1 • O( D) + CH4  CH3OH

Chang and Lin, Chem. Phys. Lett. 363 (2002) 175-181 Unimolecular dissociation unless excess vibrational energy is quenched Experimental Design for O(1D) Insertion Reactions

Gas Mixture: 92% Ar & O2, <1% O3, ~8% precursor Delay Generator Oscilloscope 1:2:3:4:5:6 Pulsed 248 nm KrF Valve Pulse Driver Excimer Laser Boxcar Boxcar Bolometer Multiplier Synthesizer 50 GHz – 1.2 THz 6 mm – 250 μm Lockin Amplifier

250 kHz – 50 GHz 1.2 km – 6 mm Experimental Design for O(1D) Insertion Reactions Ozone Depletion 1 1 O3 + hν(248 nm)  O2( Δ) + O( D) Methanol Production

1 O( D) + CH4  CH3OH Future Work

• Acquire methylamine to produce aminomethanol • Search for aminomethanol transitions • Compare laboratory spectrum to observational studies Acknowledgements

• The Widicus Weaver group, esp. Thomas Anderson • Michael Heaven for loan of laser and ozone generator • Cherry L Logan Computing Center • NASA APRA (NNX11AI07G)

N-methylhydroxylamine

Constant Calculations Experimental A (GHz) 39.1319 38.930771 B (GHz) 10.0320 9.939607 C (GHz) 8.7775 8.690716

μA (Debye) 0.663 0.611

μB (Debye) -0.444 0.366 1/2 μC (Debye) -0.038 (-0.012) ~0

Methyl rotor ~1384 cm-1 V3 found experimentally to be -1 Hydroxyl wag ~2405 cm-1 1243 cm

Sung and Harmony, 1979 Hays and Widicus Weaver, in revision