Abstract
Fresh general relationships for adiabatic free-energy surfaces (AFES) and corresponding diagrams of kinetic modes for adiabatic electrochemical electron transfer reactions are derived in the framework of an exactly solvable model for a metallic electrode with an infinitely wide conduction band. The model is a limiting case of the Anderson model applicable to the sp metals. In contrast to earlier studies of adiabatic reactions in a model for an electrode with an infinitely wide conduction band, this work accounts for the electron–electron correlation effects exactly. As an illustration, an AFES is calculated and a diagram of kinetic modes is constructed for a special case corresponding to the equilibrium electrode potential of a two-electron reaction. The exact AFES is compared with the AFES computed in the Hartree–Fock approximation and a spinless model. The correlation effects are shown to play a substantial role and lead to a considerable decrease in the activation free energy.
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Medvedev, I.G. Electron Correlations for Adiabatic Electrochemical Electron Transfer Reactions in a Model for an Electrode with an Infinitely Wide Conduction Band. Russian Journal of Electrochemistry 39, 44–53 (2003). https://doi.org/10.1023/A:1021963512659
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DOI: https://doi.org/10.1023/A:1021963512659