Effects of Electron Correlations in a Simple Model for Adiabatic Electrochemical Reactions: The General Relationships

General relationships for adiabatic free-energy surfaces (AFES) for electrochemical reactions of electron transfer are derived in the framework of exactly solvable model of the so-called surface molecule, which is a limiting case of Anderson's Hamiltonian and may be applied to transition metals. As opposed to earlier models for adiabatic reactions, the model exactly allows for the effects of electron–electron correlations. The obtained results constitute a basis for calculating AFES and plotting diagrams that correspond to different kinetic regimes of one- and two-electron processes.