title: Variational transition-state theory study of the dimethyl sulfoxide (DMSO) and OH reaction.
abstract: The mechanism for the atmospheric oxidation of DMSO has been studied. For the first time, all the possible channels in the DMSO + OH reaction are studied together theoretically, and their corresponding rate constants have been evaluated under the variational transition-state formalism. Three different channels have been characterized: an addition-elimination process to form MSIA (CH3SOOH) and CH3, a H-abstraction pathway to give CH3SOCH2 and H2O, and a nonkinetically relevant S(N)2-type reaction to form methanol and CH3SO. In agreement with previous experimental and theoretical works, the main product in the DMSO + OH reaction turns out to be the MSIA, with a branching ratio at 298.15 K around 97%. The effects of pressure in the global rate constant have also been analyzed.
authors.affiliation: Departament de Química, Universitat Autonoma de Barcelona, 08193 Bellaterra (Barcelona), Spain.
authors.forename: Núria
authors.initials: N
authors.lastname: González-García
authors.forename: Angels
authors.initials: A
authors.lastname: González-Lafont
authors.forename: José M
authors.initials: JM
authors.lastname: Lluch