Effect of hydration on the hydrogen abstraction reaction by HO in DMS and its oxidation products.
The gas-phase hydrogen abstraction reaction between the HO radical and sulfur containing species in the absence and presence of a single water molecule is investigated theoretically. The sulfur containing species dimethyl sulfide, dimethyl sulfoxide, and dimethyl sulfone are considered. The calculations are carried out with a mixture of density function theory and second order Møller-Plesset perturbation theory. We find that the energy of the hydrated transition state structures for the hydrogen abstraction reactions is lowered compared to that of the nonhydrated ones. Furthermore, the energy difference between the reaction complex and the transition state is reduced when one water molecule is added. The atmospheric abundance of the different hydrated complexes is estimated in order to assess the relative importance of the possible reaction mechanisms.
Jørgensen
Solvejg
S
Copenhagen Center for Atmospheric Chemistry, Department of Chemistry, University of Copenhagen, DK-2100 Copenhagen Ø, Denmark.
Kjaergaard
Henrik G
HG