Microscopic quantum mechanical Marcus theory for chemical reactions and its relationship to the Butler‐Volmer equation used in redox flow battery analysis

Abstract

The vanadium redox flow battery has been intensively examined since the 1970s. What is missing is a connection between the current‐overpotential Butler‐Volmer equation, which provides an extremely helpful starting point for analytical and numerical studies, and microscopic quantum mechanical behavior at the atomic level. Such a connection will allow further advancements beyond the macroscopic, though very useful and insightful, modeling already done in the literature. Here we show rigorously the connection between the Butler‐Volmer transfer coefficients, and the Marcus Gibbs free energy quantum mechanical parameters, and develop the equation directly in terms of the quantum mechanical parameters.

Keywords

Identifiers

DOI

10.1002/qua.27279

Journal

International Journal of Quantum Chemistry

Year

2023