Effects of Electronic Correlations for Adiabatic Electrochemical Reactions of Electron Transfer in Electrode Models with Nearly Empty and Nearly Filled Conduction Bands: General Relationships

Abstract

Expressions for the calculation of the adiabatic free energy surfaces (AFES) and average number of electrons in the valence orbital of the reagent for adiabatic electrochemical reactions of electron transfer are obtained in terms of exactly solved models for a metal electrode with nearly empty and nearly filled conduction bands. The models are extreme cases of the Anderson model, which account exactly for the electron–electron correlation effects. In particular, the electrode model with a nearly filled conduction band can be applied to transition metals of Group VIII in the periodic table. Exact relationships connecting AFES and diagrams of kinetic modes (DKM) for electrodes with symmetric position of Fermi levels relative to the conduction band center are obtained. Two characteristic functions for analyzing the role of electron–electron correlation effects in the system under consideration are proposed and calculated. The results form a basis for calculating AFES and studying correlation effects in adiabatic electrochemical reactions of electron transfer and constructing DKM that would correspond to different electron transfer modes.