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A chemical potential equalization approach to constant potential polarizable electrodes for electrochemical-cell
Hiroshi Nakano1, Hirofumi Sato1
1Department of Molecular Engineering, Graduate School of Engineering, Kyoto University, Kyoto 615-8510, Japan.
Abstract:
Atomistic modeling of electrochemical systems is one of the most challenging topics in the field of molecular simulations. We derive the equations for modeling constant potential polarizable electrodes in electrochemical-cell simulations based on the chemical potential equalization principle. They reduce to those derived by Siepmann and Sprik [J. Chem. Phys. 102, 511 (1995)], later arranged by Reed, Lanning, and Madden [J. Chem. Phys. 126, 084704 (2007)] under some assumptions. The present approach clarifies the physical meaning of the total energy of a system that includes classical polarizable electrodes, which is important in order to analyze the energetics of chemical phenomena at electrode-electrolyte interfaces. The effects of the Hubbard U parameter of an electrode atom are discussed in connection with the perfect conductor limit for a metal electrode.
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