Theoretical study of the CH 3SCH 2OO and CH 3SCH 2O radicals

Abstract

Ab initio calculations at the [QCISD(T)/6-31 + G(2df, p)]//MP2/6-31G(d) level have been applied to CH 3SCH 2OO, a radical which is thought to be important in the atmospheric oxidation of dimethylsulfide. The geometries of CH 3SCH 2OO and the related CH 3SCH 2O radical are similar to other organic radicals of formula RCH 2OO and RCH 2O (i.e. the SCH 3 group does not strongly affect the O 2 binding energy or geometry). Isodesmic reactions have been used to calculate heats of formation at 298 K of 5.9 and 7.4 kcal mol for CH 3SCH 2OO and CH 3SCH 2O, respectively. In both radicals, the unpaired spin density resides on the terminal oxygen.