I. G. Medvedev
Frumkin Institute of Electrochemistry, Russian Academy of Sciences, Leninskii pr. 31, Moscow, 119071 Russia
Received June 26, 2003
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 tran-
sition 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 sys-
tem under consideration are proposed and calculated. The results form a basis for calculating AFES and study-
ing correlation effects in adiabatic electrochemical reactions of electron transfer and constructing DKM that
would correspond to different electron transfer modes.
Key words: electron transfer, adiabatic electrode process, Coulomb interaction, correlation effects, Anderson
model
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