Electrolyte dynamics effect on adiabatic outersphere electron transfer reactions

Abstract

A theoretical study of the effects of electrolyte solution dynamics on adiabatic outersphere electron transfer reactions is presented. The theory is self-contained and it properly includes the diffusive and non-diffusive modes of relaxation of ions and solvent molecules. Numerical results are obtained for the rate of electron transfer in a model electrolyte solution consisting of spherical ions in Stockmayer solvent and are compared with the rate of electron transfer in the pure Stockmayer solvent. It is found that the deviation from the prediction of transition state theory is higher for electron transfer in the electrolyte solution and this is because of the extra frictional contribution from slow ion atmosphere relaxation.