AB-INITIO STUDY OF THE REACTION OF CHLORINE ATOMS WITH H2S, CH3SH, CH3SCH3 AND CS2

The geometries of adducts of Cl with H2S, CH3SH, CH3SCH3 and CS2 have been optimised in ab initio MP2(Full)/6-311G* calculations and vibrat ional frequencies have been calculated. The strength of bonding increa ses along the series H2S, CH3SH, CH3SCH3 with the replacement of a hyd rogen by CH3 increasing the binding energy by ca. 25 kJ mol(-1). Trans ition states for the hydrogen abstraction reactions for Cl with H2S an d 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 importa nt in the case of Cl + CH3SH.