Abstract
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.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
REFERENCES
Ziman, J.M., Principles of the Theory of Solids, London: Cambridge Univ. Press, 1972.
Dogonadze, R.R. and Chizmadzhev, Yu.A., Dokl. Akad. Nauk SSSR, 1962, vol. 144, p. 1077.
. Kuznetsov, A.M., Charge Transfer in Physics, Chemistry, and Biology, Reading: Gordon & Breach, 1995.
Kuznetsov, A.M. and Ulstrup, J., Electron Transfer in Chemistry and Biology, Chichester: Wiley, 1999.
Hush, N.S., J. Electroanal. Chem., 1999, vol. 460, p. 5.
Sutin, N., Adv. Chem. Phys., 1999, vol. 106, p. 7.
Dogonadze, R.R., Kuznetsov, A.M., and Vorotyntsev, M.A., J. Electroanal. Chem., 1970, vol. 25, p. 17.
Dogonadze, R.R., Kuznetsov, A.M., and Vorotyntsev, M.A., Croat. Chem. Acta, 1972, vol. 44, p. 257.
Kuznetsov, A.M., J. Electroanal. Chem., 1983, vol. 159, p. 241.
Schmickler, W., J. Electroanal. Chem., 1986, vol. 204, p. 31.
Sebastian, K.L., J. Chem. Phys., 1989, vol. 90, p. 5056.
Boroda, Yu.G. and Voth, G.A., J. Chem. Phys., 1996, vol. 104, p. 6168.
Schmickler, W., Electrochim. Acta, 1996, vol. 14, p. 2329.
Koper, M.T.M. and Schmickler, W., J. Electroanal. Chem., 1998, vol. 450, p. 83.
Koper, M.T.M. and Voth, G.A., Chem. Phys. Lett., 1998, vol. 282, p. 100.
Calhoun, A., Koper, M.T.M., and Voth, G.A., Chem. Phys. Lett., 1999, vol. 305, p. 94.
Schmickler, W. and Koper, M.T.M., Electrochem. Commun., 1999, vol. 1, p. 406.
Kuznetsov, A.M., Medvedev, I.G., and Ulstrup, J., Electrochem. Commun., 2000, vol. 2, p. 135.
Muscat, J.P. and Newns, D.M., Prog. Surf. Sci., 1978, vol. 9, p. 1.
Boroda, Yu.G. and Voth, G.A., J. Electroanal. Chem., 1998, vol. 450, p. 95.
Einstein, T.L., Hertz, J.A., and Schrieffer, J.A., Theory of Chemisorption, vol. 19 of Topics in Current Physics, Smith, J.R., Ed., Berlin: Springer, 1980.
Morrison, S.R., The Chemical Physics of Surfaces, New York: Plenum, 1977.
Medvedev, I.G., Surf. Sci., 1992, vol. 274, p. 393.
Anderson, P.W., Phys. Rev., 1961, vol. 124, p. 41.
Kornyshev, A.A. and Schmickler, W., J. Electroanal. Chem., 1985, vol. 185, p. 253.
Brenig, W. and Schönhammer, K., Z. Phys. B: Condens. Matter, 1974, vol. 267, p. 201.
Einstein, T.L., Phys. Rev. B, 1975, vol. 11, p. 577.
Volokitin, A.I., Fiz. Tverd. Tela (Leningrad), 1978, vol. 20, p. 1206.
Medvedev, I.G., J. Phys: Condens. Matter, 1997, vol. 9, p. 4129.
Medvedev, I.G., Khim. Fiz., 1986, vol. 5, p. 442.
Medvedev, I.G., Elektrokhimiya, 1993, vol. 29, p. 1107.
Schönhammer, K., Phys. Rev. B, 1976, vol. 13, p. 4336.
Dworin, L., Phys. Rev., 1967, vol. 164, p. 818.
Kuznetsov, A.M., Stochastic and Dynamic Views on Chemical Reaction Kinetics in Solutions, Lausanne: Presses Polytechniques et Universitaires Romandes, 1999.
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Kuznetsov, A.M., Medvedev, I.G. Effects of Electron Correlations in a Simple Model for Adiabatic Electrochemical Reactions: The General Relationships. Russian Journal of Electrochemistry 37, 335–340 (2001). https://doi.org/10.1023/A:1016606603869
Issue Date:
DOI: https://doi.org/10.1023/A:1016606603869