Potential Dependence of Electrochemical Barriers from ab Initio Calculations

We present a simple and computationally efficient method to determine the potential dependence of the activation energies for proton–electron transfer from a single ab initio barrier calculation. We show that the potential dependence of the activation energy is given by the partial charge transferred at the transition state. The method is evaluated against the potential dependence determined explicitly through multiple calculations at varying potential. We show that the transfer coefficient is given by the charge transferred from the initial to transition state, which has significant implications for electrochemical kinetics.