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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

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Abstract

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.

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Authors and Affiliations

  1. Frumkin Institute of Electrochemistry, Russian Academy of Sciences, Leninskii pr. 31, Moscow, 119071, Russia

    A. M. Kuznetsov & I. G. Medvedev

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  1. A. M. Kuznetsov
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  2. I. G. Medvedev
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Kuznetsov, A.M., Medvedev, I.G. 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. Russian Journal of Electrochemistry 39, 990–998 (2003). https://doi.org/10.1023/A:1025784206966

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  • DOI: https://doi.org/10.1023/A:1025784206966

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