Journal of Electroanalytical Chemistry, Vol.655, No.1, 65-72, 2011
On the evaluation and analysis of the Marcus-Hush-Chidsey integral
Chidsey's implementation of the electron-exchange theories of Marcus and Hush leads to a prediction of the potential-dependence of electrochemical rate constants that is couched in terms of unfriendly integrals. Here we perform the integrations and recast the resulting series into formulas that are more easily enumerated and manipulated. Thereby, several observations are made concerning rate constants that follow the Marcus-Hush-Chidsey theory, and contrasted with the predictions of the Butler-Volmer model. (C) 2011 Elsevier B.V. All rights reserved.
Keywords:Marcus-Hush;Butler-Volmer;Electrode kinetics;Rate constant;Overvoltage;Reorganization energy