Simulation of Benzenesulfonyl Chloride Hydrolysis. Influence of the Size and Structural Ordering of Aqueous Clusters on Thermodynamic and Activation Parameters of the Process

Abstract

The potential energy surfaces for hydrolysis of benzenesulfonyl chloride in clusters incorporating one to three additional water molecules (along with the molecule acting as nucleophile) were calculated by the PM3 method in the supermolecular approximation. As in the gas phase, hydrolysis of benzenesulfonyl chloride in clusters is a two-step exothermic process occurring via relatively unstable five-coordinate inter- mediate. The structural and thermodynamic parameters of the intermediate and transition states of the reaction, and also the thermodynamic functions of the process were calculated for seven clusters of different structures.