Electron correlation effects for adiabatic electrochemical reactions of electron transfer in a model for an electrode with an infinitely wide conduction band: Computing adiabatic free energy surfaces

The adiabatic free energy surfaces for adiabatic electrochemical reactions of electron transfer are calculated in a model for an electrode with an infinitely wide conduction band with exact allowance for electron-electron correlations. The surfaces are analyzed on the basis of a diagram of kinetic modes obtained earlier. It is shown that, as in a surface-molecule model for these reactions, the correlation effects play an essential role and lead to a considerable decrease in the activation free energies and to qualitatively different forms of adiabatic free energy surfaces in certain ranges of model parameters.