Reaction mechanism and kinetics for the oxidation of dimethyl sulfide by nitrate radical

Abstract

The reaction between dimethyl sulfide (CH 3SCH 3) and nitrate radical (NO 3) is studied using density functional theory and ab initio methods. The transition state for this reaction is optimized at different levels of theory and basis sets, and then used for kinetics calculations of the rate constant. The CH 3SCH 3 + NO 3 reaction leading to CH 3SCH 2 and HNO 3 is shown to have a negative activation energy and thus negative temperature dependence. The study confirms that the NO 3 radical is a significant contributor to the oxidation of DMS in the troposphere.