KINETICS OF THE H2O-PHASE AND IN SOLUTION BY AN INSERTION MECHANISM(CCL2 REACTION IN GAS)

The single-step insertion reaction of dichlorocarbene into the water O H bond was investigated at the ab initio level of theory. We have used additivity approximation to obtain an effective CCSD(T)/cc-pVTZ + dif f single-point energy calculation on MP2/DZP optimized geometries. The solvent effect on the activation free energy was included by performi ng Monte Carlo simulations and statistical perturbation theory. it was found that direct insertion should not play an important role in the H2O + CCl2 reaction. A mechanism involving two water molecules is sugg ested as a possible alternative reaction pathway. (C) 1998 Elsevier Sc ience B.V.