Crossed-beam reaction of carbon atoms with sulfur containingmolecules I: chemical dynamics of thioformyl (HCS;X2A') formation fromreaction of C(3pj) with hydrogen sulfide, H2S (x1A1)
The reaction between ground state carbon atoms, C(3Pj), andhydrogen sulfide, H2S(X1A1), was studied at four average collisionenergies between 16.7 and 42.8 kJ mol-1 using the crossed molecular beamtechnique. The reaction dynamics were deducted from time-of-flightspectra and from laboratory angular distributions combined with ab initiocalculations. These data suggest that the reaction proceeds through anaddition of C(3Pj) to the sulfur atom to form a triplet CSH2 van derWaals complex. Successive H atom migration on the triplet or singletsurface forms a thiohydroxycarbene intermediate, HCSH, which decomposesthrough a tight exit transition state to HCS(X2A[prime]) + H(2S1/2). Atlower collision energies, a weak L-L[prime]coupling leads to isotropiccenter-of-mass angular distributions. As the collision energy rises, theangular distributions show increasing forward scattering therebydocumenting that the reaction goes through an osculating HCSH complex.Identification of the HCS isomer under single collision conditions is apotential one-step pathway by which to form organo-sulfur molecules ininterstellar environments during the collision of the cometShoemaker-Levy 9 with Jupiter, and in combustion flames of sulfurcontaining fuels.
- Research Organization:
- Ernest Orlando Lawrence Berkeley NationalLaboratory, Berkeley, CA (US)
- Sponsoring Organization:
- USDOE Director, Office of Science
- DOE Contract Number:
- AC02-05CH11231
- OSTI ID:
- 907892
- Report Number(s):
- LBNL--45153
- 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
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