Monte Carlo simulations of heterogeneous electron transfer: New challenges

A. S. Berezin A. S. Berezin , R. R. Nazmutdinov R. R. Nazmutdinov
Российский электрохимический журнал
Abstract / Full Text

We report results of MC simulations of electron transfer across a metal electrode/electrolyte solution interface. The model presumes the Landau–Zener theory and a random walk on a two-dimensional lattice formed by crossing parabolic reaction free energy surfaces along the solvent coordinate. Emphasis is put on investigating the activationless discharge regime; the bridge-assisted electron transfer is also partially addressed. We have calculated effective electronic transmission coefficient as a function of the electrode overpotential and temperature in a wide range of orbital overlap. The dependence of the transmission coefficient on the electronic density of states is analyzed as well.

Author information
  • Kazan National Research Technological University, Kazan, 420015, Russia

    A. S. Berezin & R. R. Nazmutdinov

  1. Levich, V.G., Kinetics of Reactions with Charge Transfer, in Physical Chemistry, an Advanced Treatise, Eyring, H., Henderson, D., and Jost, W., Eds., N.Y.: Acad. Press, 1970, vol. Xb.
  2. Dogonadze, R.R. and Kuznetsov, A.M., Progress in Surface Science, 1975, vol. 6, pp. 1–41.
  3. Kuznetsov, A.M., Charge Transfer in Physics, Chemistry and Biology. Mechanisms of Elementary Processes and Introduction to the Theory, Berkshire: Gordon and Breach Science Publishers, 1995.
  4. Kuznetsov, A.M. and Ulstrup, J., Electron Transfer in Chemistry and Biology, Chichester, UK: Wiley, 1999.
  5. Kuznetsov, A.M., Nazmutdinov, R.R., and Schmickler, W., Monte Carlo simulations of the electrochemical electron transfer processes, J. Electroanal. Chem., 2002, vol. 532, pp. 171–180.
  6. Kokkanen, A.A., Kuznetsov, A.M., and Medvedev I.G., Approximate method for calculation of electron transition probability for simple outer-sphere electrochemical reactions, Russ. J. Electrochem., 2008, vol. 44, pp. 397–407.
  7. Nazmutdinov, R.R., Glukhov, D.V., Tsirlina, G.A., and Petrii, O.A., Activationless reduction of a hexacyanoferrate anion at a mercury electrode, Russ. J. Electrochem., 2003, vol. 39, pp. 97–107.
  8. Nazmutdinov, R.R., Glukhov, D.V., Tsirlina, G.A., and Petrii, O.A., Molecular description of the persulphate ion reduction on a mercury electrode, Russ. J. Electrochem., 2002, vol. 38, pp. 720–731.
  9. Nazmutdinov, R.R., Bronshtein, M.D., Zinkicheva, T.T., and Glukhov, D.V., Modeling of electron transfer across electrochemical interfaces: State-of-the art and challenges for quantum and computational chemistry, Int. J. Quantum Chem., 2016, vol. 116, pp. 189–201.
  10. Marcus, R.A., On the theory of oxidation-reduction reactions involving electron transfer. I., J. Chem. Phys., 1956, vol. 24, pp. 966–978.
  11. Iwasita, T.I., Schmickler, W., and Schultze, J.W., Influence of the metal on the kinetics of outer sphere redox reactions, Berichte der Bunsenges. Phys. Chem. Chem. Phys., 1985, vol. 89, pp. 138–142.
  12. Feldberg, S.W. and Sutin, N., Distance dependence of heterogeneous electron transfer through the nonadiabatic and adiabatic regimes, Chem. Phys., 2006, vol. 324, pp. 216–225.
  13. Kornyshev, A.A., Kuznetsov, A.M., and Ulstrup, J., Effect of overpotential on the electronic tunnel factor in diabatic electrochemical processes, J. Phys. Chem., 1994, vol. 98, pp. 3832–3837.
  14. Nazmutdinov, R.R., Schmickler, W., and Kuznetsov, A.M., Microscopic modeling of the reduction of a Zn(II) aqua-complex on metal electrodes, Chem. Phys., 2005, vol. 109, pp. 257–268.
  15. Zhang, J., Chi, Q., Nazmutdinov, R.R., Zinkicheva, T.T., and Bronshtein, M.D., Submolecular electronic mapping of single cysteine molecules by in situ scanning tunneling imaging, Langmuir, 2009, vol. 25, pp. 2232–2240.
  16. Mohr, J. and Schmickler, W., Exactly solvable quantum model for electrochemical electron transfer reactions, Phys. Rev. Lett., 2000, vol. 85, pp. 1051–1054.
  17. Schmickler, W. and Mohr, J., The rate of electrochemical electron transfer reactions, J. Chem. Phys., 2002, vol. 117, pp. 2867–2872.
  18. Schmickler, W., The rate of electron transfer reactions in the diffusive limit, Cond. Matt. Phys., 2001, vol. 4, pp. 773–778.