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

Abstract

The geometries of adducts of Cl with H₂S, CH₃SH, CH₃SCH₃ and CS₂ 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 H₂S, CH₃SH, CH₃SCH₃ with the replacement of a hydrogen by CH₃ increasing the binding energy by ca. 25 kJ mol^-1. Transition states for the hydrogen abstraction reactions for Cl with H₂S and CH₃SH have been located at the same level of theory. In the case of H₂S, hydrogen abstraction could make a significant contribution to the reaction. The hydrogen-abstraction reaction is expected to be important in the case of Cl+CH₃SH.

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