EFFECTS OF ION ATMOSPHERE RELAXATION ON DIPOLE ISOMERIZATION-REACTIONS IN ELECTROLYTE-SOLUTIONS

A theoretical study of the effects of ion atmosphere relaxation on the rate of a model dipole isomerization reaction in electrolyte solution s is presented. The time-dependent ion atmosphere friction is calculat ed by using a molecular hydrodynamic theory which properly includes th e static and dynamic interionic correlations through ionic structure f actors and van Hove functions. The rate constant is determined by empl oying the well-known Grote-Hynes theory. Numerical results are obtaine d for the time-dependent ion atmosphere friction and for the rate of i somerization reaction in electrolyte solutions of varying ion concentr ation and dielectric constant. It is found that the ion atmosphere fri ction can have significant effects in reducing the rate of isomerizati on below the prediction of equilibrium solvation transition state theo ry. (C) 1998 Elsevier Science B.V.