Crossed-beam reaction of carbon atoms with sulfur containing molecules. I. Chemical dynamics of thioformyl (HCS;X{sup 2}A{sup {prime}}) formation from reaction of C({sup 3}P{sub j}) with hydrogen sulfide, H{sub 2}S(X{sup 1}A{sub 1})

Journal Article · Mon Feb 01 00:00:00 EST 1999 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.477944· OSTI ID:326859

Kaiser, R I; Ochsenfeld, C; Head-Gordon, M; Lee, Y T ^[1]

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1. Department of Chemistry, University of California, Berkeley, California 94720 (United States)

The reaction between ground state carbon atoms, C({sup 3}P{sub j}), and hydrogen sulfide, H{sub 2}S(X{sup 1}A{sub 1}), was studied at four average collision energies between 16.7 and 42.8 kJ mol{sup {minus}1} using the crossed molecular beam technique. The reaction dynamics were deducted from time-of-flight spectra and from laboratory angular distributions combined with {ital ab initio} calculations. These data suggest that the reaction proceeds through an addition of C({sup 3}P{sub j}) to the sulfur atom to form a triplet CSH{sub 2} van der Waals complex. Successive H atom migration on the triplet or singlet surface forms a thiohydroxycarbene intermediate, HCSH, which decomposes through a tight exit transition state to HCS(X{sup 2}A{sup {prime}})+H({sup 2}S{sub 1/2}). At lower collision energies, a weak {bold L-L}{sup {prime}} coupling leads to isotropic center-of-mass angular distributions. As the collision energy rises, the angular distributions show increasing forward scattering thereby documenting that the reaction goes through an osculating HCSH complex. Identification of the HCS isomer under single collision conditions is a potential one-step pathway by which to form organo-sulfur molecules in interstellar environments during the collision of the comet Shoemaker-Levy 9 with Jupiter, and in combustion flames of sulfur containing fuels. {copyright} {ital 1999 American Institute of Physics.}

• OSTI ID: 326859
• Journal Information: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 5 Vol. 110; ISSN JCPSA6; ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

40 CHEMISTRY
ATOMIC BEAMS
CARBON
CHEMICAL REACTION KINETICS
GROUND STATES
HYDROGEN SULFIDES
MOLECULAR BEAMS
ORGANIC COMPOUNDS
ORGANIC SULFUR COMPOUNDS
RADICALS
TIME-OF-FLIGHT METHOD