A kinetic model of electron transfer at the electrode-electrolyte interface: Statistical mechanics and electrochemical aspects
Abstract
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.
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BibTeX
@misc{velozadiaz2026kinetic,
title = {{A kinetic model of electron transfer at the electrode-electrolyte interface: Statistical mechanics and electrochemical aspects}},
author = {Diego Veloza-Diaz and Robinson Cortes-Huerto and Pietro Ballone and Nancy C. Forero-Martinez},
howpublished = {arXiv},
year = {2026},
month = sep,
doi = {10.48550/arxiv.2609.28768},
eprint = {2609.28768},
archivePrefix = {arXiv},
url = {https://arxiv.org/abs/2609.28768},
note = {CC BY-NC-ND 4.0},
}
RIS
TY - UNPB
TI - A kinetic model of electron transfer at the electrode-electrolyte interface: Statistical mechanics and electrochemical aspects
AU - Diego Veloza-Diaz
AU - Robinson Cortes-Huerto
AU - Pietro Ballone
AU - Nancy C. Forero-Martinez
PY - 2026
DA - 2026/09/23
PB - arXiv
DO - 10.48550/arxiv.2609.28768
UR - https://arxiv.org/abs/2609.28768
AB - 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.
ER -