Ab initio study of the reaction of chlorine atoms with H2S, CH3SH, CH3SCH3 and CS2

Abstract

The geometries of adducts of Cl with H 2 S, CH 3 SH, CH 3 SCH 3 and CS 2 have been optimised in ab initio MP2(Full)/6-311G** calculations and vibrational frequencies have been calculated. The strength of bonding increases along the series H 2 S, CH 3 SH, CH 3 SCH 3 with the replacement of a hydrogen by CH 3 increasing the binding energy by ca. 25 kJ mol -1 . Transition states for the hydrogen abstraction reactions for Cl with H 2 S and CH 3 SH have been located at the same level of theory. In the case of H 2 S, hydrogen abstraction could make a significant contribution to the reaction. The hydrogen-abstraction reaction is expected to be important in the case of Cl+CH 3 SH.