Ab Initio Kinetics of Electrochemical Reactions Using the Computational Fc0/Fc+ Electrode

The current state-of-the-art electron-transfer modeling primarily focuses on the kinetics of charge transfer between an electroactive species and an inert electrode. Experimental studies have revealed that the existing Butler–Volmer model fails to satisfactorily replicate experimental voltammetry results for both solution-based and surface-bound redox couples. Consequently, experimentalists lack an accurate tool for predicting electron-transfer kinetics. In response to this challenge, we developed a density functional theory-based approach for accurately predicting current peak potentials by using the Marcus–Hush model. Through extensive cyclic voltammetry simulations, we conducted a thorough exploration that offers valuable insights for conducting well-informed studies in the field of electrochemistry.