Understanding Electrochemical Reversibility using Density Functional Theory: Bridging Theoretical Scheme of Squares and Experimental Cyclic Voltammetry

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 enhanced our understanding of electrochemical reactions by leveraging the scheme of squares framework using a set of tens of molecules that have been examined in the field of redox flow batteries. Furthermore, we focused on developing our computational models by calibrating the calculated redox potentials against experimental data, thereby enhancing the predictive performance of our approach. These findings are applicable to a wide range of applications from energy storage to medicine and synthetic chemistry.