Constant Potential, Electrochemically Active Boundary Conditions for Electrochemical Simulation

This manuscript presents a theoretical model for simulating molecular dynamics at electrode-electrolyte interfaces. The novelty of the model is that it combines a method for simulating constant potential electrodes and a method for simulating stochastic interfacial charge transfer. We combine these methods to simulate model electrochemical systems under driven conditions, where charge is flowing across the electrode-electrolyte interface. The manuscript describes the theoretical formalism and applies it to a model battery system. We highlight the ability of the model to support the formation of electrical double-layers and to provide microscopic physical insight the results of potential jump experiments.