THE ENERGY OF THE SOLVENT REORGANIZATION AND THE ACTIVATION-ENERGY FOR NONADIABATIC REACTIONS OF ELECTRON AND PROTON-TRANSFER IN HETEROGENEOUS MEDIA WITH SPATIAL-DISPERSION

In the framework of the microscopic approach, an expression is derived for the reorganization energy of the solvent in a heterogeneous mediu m with a spatial dispersion. The expression incorporates two generally distinct inductions of the electric field of reacting ions, the induc tions being generated upon a slow and a fast turning on of the field. The inertial polarization of the medium is shown to also contain the f raction of the polarization of the electrode electrons, which adiabati cally follows the inertial polarization of the solvent. The expression for the activation energy of the electrode reaction proceeding with f ormation of a neutral species is studied. According to the results of known calculations, at small distances, the attraction of the reacting ion to the electrode is prevailing; however, it follows from the expr ession obtained that, as the ion approaches the electrode, the activat ion energy for the reaction of electron or proton transfer decreases.