Ab initio molecular dynamics simulations on the hydrolysis of methyl chloride with explicit consideration of three water molecules

Ab initio molecular dynamics (MD) simulations were performed on the hydrolysis of methyl chloride (CH3Cl) with explicit consideration of three water molecules to understand the dynamics of the reaction and the role of solvent molecules in S(N)2 reactions in solution. The simulations clearly showed the existence and dynamical characteristics of two nearly concerted proton transfers involving the attacking water molecule and the solvent water molecules on the way to formation of the products. Observation of these proton transfers points clearly to the need for an explicit quantum chemical treatment of at least a few solvent water molecules to describe methyl chloride solvolysis. (C) 1998 Elsevier Science B.V. All rights reserved.