Kinetics of the H2O+CCl2 reaction in gas phase and in solution by an insertion mechanism

The single-step insertion reaction of dichlorocarbene into the water OH bond was investigated at the ab initio level of theory. We have used additivity approximation to obtain an effective CCSD(T)/cc-pVTZ+diff single-point energy calculation on MP2/DZP optimized geometries. The solvent effect on the activation free energy was included by performing 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 suggested as a possible alternative reaction pathway.