Simple formula for Marcus–Hush–Chidsey kinetics
Name
Bazant_EMB until Dec 1, 2016 Simple formula for Marcus.pdf
Size
342.33 KB
Format
Adobe PDF
Checksum (MD5)
a06dedc2f8cde73162df12ece3322909
Author(s)
Zeng, Yi
Smith, Raymond Barrett
Bai, Peng
Bazant, Martin Z
Date Issued
October 2014
Journal
Journal of Electroanalytical Chemistry
Publisher
Elsevier
Citation
Zeng, Yi et al. “Simple Formula for Marcus–Hush–Chidsey Kinetics.” Journal of Electroanalytical Chemistry 735 (2014): 77–83.
Version
Original manuscript
Abstract
The Marcus–Hush–Chidsey (MHC) model is well known in electro-analytical chemistry as a successful microscopic theory of outer-sphere electron transfer at metal electrodes, but it is unfamiliar and rarely used in electrochemical engineering. One reason may be the difficulty of evaluating the MHC reaction rate, which is defined as an improper integral of the Marcus rate over the Fermi distribution of electron energies. Here, we report a simple analytical approximation of the MHC integral that interpolates between exact asymptotic limits for large overpotentials, as well as for large or small reorganization energies, and exhibits less than 5% relative error for all reasonable parameter values. This result enables the MHC model to be considered as a practical alternative to the ubiquitous Butler–Volmer equation for improved understanding and engineering of electrochemical systems.
MIT Department
Massachusetts Institute of Technology. Department of Chemical Engineering
Massachusetts Institute of Technology. Department of Mathematics
Terms of Use
Creative Commons Attribution-NonCommercial-NoDerivs License
Persistent DSpace Link
DOI of Published Version
https://doi.org/10.1016/j.jelechem.2014.09.038
