Understanding electrochemical reactions using density functional theory: the bridging theoretical scheme of squares and experimental cyclic voltammetry

Abstract

Mechanistic redox and acid–base reactions play pivotal roles in numerous applications in both chemistry and biology. Bridging the gap between computational insights and experimental observations is crucial to illuminate the mechanisms underlying these redox processes. In this study, we investigate electrochemical reactions by using the scheme of squares framework for a set of tens of molecules that have been examined for redox flow batteries. Furthermore, we focused on developing our computational models by calibrating the calculated redox potentials against experimental data, thereby enhancing the predictive accuracy of our approach. These findings are relevant across a wide range of applications from energy storage to medicine and synthetic chemistry.