Influence of Nonlocal Effects on Kinetic Parameters of Heterogeneous Charge Transfer Reactions

Abstract

The influence of the spatial dispersion of the solvent and of the effect of the electrical field penetration into a metal on the free energy of the solvent reorganization and the activation free energy for heterogeneous charge transfer reactions is studied. The calculations are based on the exactly solved model of a sharp metal/electrolyte interface, the model of a Born sphere for the ion, and the three-mode approximation for the dielectric function of the solvent. In the sharp-interface model, in the case of a mirror reflection, a relationship for the dielectric tensor of a heterogeneous system comprising two contacting media with a plane interface is obtained, along with an expression for the potential created by a point charge. This expression formally coincides with the expression derived earlier by Vorotyntsev and Kornyshev, but it contains true bulk dielectric functions of contacting media. In the model of the Born sphere for the ion and the three-mode approximation for the dielectric function of the solvent, an expression for the potential of image forces, which determines the dependence of the solvent reorganization energy on the distance from the reacting ion to the electrode, is obtained. It is shown that both the reorganization energy and the activation free energy decrease with decreasing distance from the ion to the electrode. The calculation results are compared with estimates of the reorganization energy obtained from experimental data for the reaction Fe3+/Fe2+ and the reaction of the hydronium ion discharge.