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The authors formulate a statistical mechanical simulation framework that unifies interfacial electron transfer with charge and mass transport across non-ideal electrode-electrolyte interfaces. Resolving the microscopic coupling between interfacial kinetics and bulk transport has historically required heuristic corrections, bottlenecking high-fidelity modeling of batteries and electrolytic cells. Crucially, the model derives fundamental non-equilibrium electrochemical relations—including Butler-Volmer kinetics, Tafel equations, and entropy production—from first principles without phenomenological tuning, while explicitly capturing the effects of fluctuating electric fields.
Classical Butler-Volmer and Tafel kinetics emerge naturally from first principles rather than ad-hoc parameter fitting once interfacial electron transfer is coupled directly to non-equilibrium electrolyte transport.
A new simulation approach ({\it J. Chem. Phys.} {\bf 163}, 164113), based on the seamless combination of the electron transfer at the electrode/electrolyte interface with the charge and mass transport in electrolyte solutions, holds the promise to advance the comprehensive modeling of basic electrochemical devices such as electrolytic cells and batteries. The underlying model also includes a fully consistent treatment of structural, thermodynamic and statistical properties of the electrical double-layer at non-ideal electron-conducting interfaces. As a result, subtle aspects such as Tafel and Butler-Volmer equations, the overpotential concept, as well as (stationary) non-equilibrium features such as the entropy production, arise naturally from the model, with a minimum of ad-hoc assumptions and elaborations of the simulation results. We illustrate these aspects for a simple model of electrochemical interface, and discuss further improvements of the method meant to enhance its ability to model systems and phenomena of interest for electrochemistry. One such improvement, concerning the effect of fluctuating electric fields on the electron transfer rate, is explicitly developed.