Effects of ion atmosphere relaxation on dipole isomerization reactions in electrolyte solutions

Abstract

A theoretical study of the effects of ion atmosphere relaxation on the rate of a model dipole isomerization reaction in electrolyte solutions is presented. The time-dependent ion atmosphere friction is calculated by using a molecular hydrodynamic theory which properly includes the static and dynamic interionic correlations through ionic structure factors and van Hove functions. The rate constant is determined by employing the well-known Grote-Hynes theory. Numerical results are obtained for the time-dependent ion atmosphere friction and for the rate of isomerization reaction in electrolyte solutions of varying ion concentration and dielectric constant. It is found that the ion atmosphere friction can have significant effects in reducing the rate of isomerization below the prediction of equilibrium solvation transition state theory.