title: Potential Dependence of Electrochemical Barriers from ab Initio Calculations.
abstract: 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.
authors.affiliation: SUNCAT Center for Interface Science and Catalysis, Department of Chemical Engineering, Stanford University , Stanford, California 94305, United States.|SUNCAT Center for Interface Science and Catalysis, SLAC National Accelerator Laboratory , Menlo Park, California 94025, United States.
authors.forename: Karen
authors.initials: K
authors.lastname: Chan
authors.affiliation: SUNCAT Center for Interface Science and Catalysis, Department of Chemical Engineering, Stanford University , Stanford, California 94305, United States.|SUNCAT Center for Interface Science and Catalysis, SLAC National Accelerator Laboratory , Menlo Park, California 94025, United States.
authors.forename: Jens K
authors.initials: JK
authors.lastname: Nørskov