A Computationally Efficient Treatment of Polarizable Electrochemical Cells Held at a Constant Potential

MK Petersen and R Kumar and HS White and GA Voth, JOURNAL OF PHYSICAL CHEMISTRY C, 116, 4903-4912 (2012).

DOI: 10.1021/jp210252g

A computationally efficient method is presented for the treatment of electrostatic interactions between polarizable metallic electrodes held at a constant potential and separated by an electrolyte. The method combines a fluctuating uniform electrode charge with explicit image charges to account for the polarization of the electrode by the electrolyte, and a constant uniform charge added to the fluctuating uniform electrode charge to account for the constant potential condition. The method is then used to calculate electron transport rates using Marcus theory and these rates are incorporated in a Kinetic Monte Carlo - Molecular Dynamics simulation scheme to efficiently model oxidation/reduction reactions in an electrochemical cell.

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