Effects of Electron Correlations in a Simple Model for Adiabatic Electrochemical Reactions: The Diagram of Kinetic Regimes

Abstract

In the framework of the surface-molecule model for adiabatic electrochemical reactions of electron transfer previously suggested by the authors, a diagram of kinetic regimes (DKM) in the space of model parameters is obtained. The diagram comprises critical regions that correspond to various feasible electron transfer processes (transfer of one electron, simultaneous transfer of two electrons, transfer of two electrons in the presence of an intermediate state) and a region corresponding to electroadsorption of the reagent in certain charge states. Analytical expressions for boundary curves of DKM are obtained for a number of simple cases. A DKM for the general case of the surface-molecule model with an exact allowance for electron–electron correlations is constructed and analyzed.