Extension of solution-reaction-surface description to examination of nonequilibrium solvation effect for microsolvated reaction

摘要

A microscopic method to examine a nonequilibrium solvation effect is reported. The solution reaction is simplified as a barrier-crossing reaction within a solution reaction surface that corresponds to a two-dimensional space determined by solute and solvent reactive coordinates. For this simplification, the motions within the space spanned by nonreactive coordinates are frozen. We derive three rate constant expressions: (1) in the nonadiabatic solvation limit, (2) in the equilibrium solvation limit, and (3) of the transition-state theory. This method was applied to the examination of the contact-ion-pair formation of t-BuCl in four waters. We found that the nonadiabatic solvation picture overestimates the nonequilibrium solvation effect. (C) 2000 John Wiley & Sons, Inc. [References: 18]