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J. Phys. Soc. Jpn. 68, pp. 3729-3737 (1999) [9 Pages]
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Monte Carlo Simulation Study on the Structure and Reaction at Metal-Electrolyte Interface. II. Mechanism of Nonlinear Electrode Reactions

Norikazu Goto1, Toshiaki Kakitani1, Takahisa Yamato1, and Yasuyo Hatano2
+ Affiliations
1Department of Physics, Graduate School of Science, Nagoya University, Furo-cho, Chikusa-ku, Nagoya 464-8602 2School of Computer and Cognitive Science, Chukyo University, Toyota, Aichi 470-0389
Received November 5, 1998

Using the two-dimensional free energy surfaces which were obtained previously by the Monte Carlo simulations for metal-electrolyte interfaces by allowing the movement of reactant [N. Goto et al. : J. Phys. Soc. Jpn. 66 (1997) 1825], we have analyzed the mechanism of nonlinearity in the electrode reaction in detail. The nonlinearity was defined as a square of ratio between widths of the energy gap laws for the neutralization and ionization reactions. We developed a method to derive the nonlinearity due to only fluctuations of motion of solvent molecules and electrolyte ions for each distance of the reactant from the metal surface. We found that the nonlinearity was the largest (4.8) at the distance 6 Å of the reactant from the metal surface, and was the smallest (2.2) at the distance 2 Å where the reactant is in contact with the metal surface and at the distance larger than 9 Å where Gouy-Chapman diffuse layer ends. We also found that the movement of the ions and solvents directly adsorbed to the metal-surface is strongly restricted, showing a feature of dielectric saturation. Combining these facts, we conclude that the strongly adsorbed layer of ions and solvent molecules (Helmholtz double layer) causes a large nonlinear phenomenon of the electrode reaction due to breakdown of the central limit theorem especially for the reactant contacting the adsorbed layer.

©1999 The Physical Society of Japan
https://doi.org/10.1143/JPSJ.68.3729
KEYWORDS: nonlinear electrode reaction, nonlinear fluctuation, metal-electrolyte interface, Helmholtz double layer, electron transfer, energy gap law, electrolyte, central limit theorem, Marcus theory

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