Simple formula for Marcus–Hush–Chidsey kinetics
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 reac...
| Main Authors: | , , , |
|---|---|
| Other Authors: | |
| Format: | Article |
| Language: | en_US |
| Published: |
Elsevier
2017
|
| Online Access: | http://hdl.handle.net/1721.1/107632 https://orcid.org/0000-0003-2421-6781 |
| _version_ | 1826205817546735616 |
|---|---|
| author | Zeng, Yi Smith, Raymond Barrett Bai, Peng Bazant, Martin Z |
| author2 | Massachusetts Institute of Technology. Department of Chemical Engineering |
| author_facet | Massachusetts Institute of Technology. Department of Chemical Engineering Zeng, Yi Smith, Raymond Barrett Bai, Peng Bazant, Martin Z |
| author_sort | Zeng, Yi |
| collection | MIT |
| description | 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. |
| first_indexed | 2024-09-23T13:19:54Z |
| format | Article |
| id | mit-1721.1/107632 |
| institution | Massachusetts Institute of Technology |
| language | en_US |
| last_indexed | 2024-09-23T13:19:54Z |
| publishDate | 2017 |
| publisher | Elsevier |
| record_format | dspace |
| spelling | mit-1721.1/1076322022-10-01T14:34:47Z Simple formula for Marcus–Hush–Chidsey kinetics Zeng, Yi Smith, Raymond Barrett Bai, Peng Bazant, Martin Z Massachusetts Institute of Technology. Department of Chemical Engineering Massachusetts Institute of Technology. Department of Mathematics Zeng, Yi Smith, Raymond Barrett Bai, Peng Bazant, Martin Z 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. National Science Foundation (U.S.). Graduate Research Fellowship Program (Grant 1122374) Samsung-MIT Alliance 2017-03-22T14:16:55Z 2017-03-22T14:16:55Z 2014-10 2014-09 Article http://purl.org/eprint/type/JournalArticle 1572-6657 http://hdl.handle.net/1721.1/107632 Zeng, Yi et al. “Simple Formula for Marcus–Hush–Chidsey Kinetics.” Journal of Electroanalytical Chemistry 735 (2014): 77–83. https://orcid.org/0000-0003-2421-6781 en_US http://dx.doi.org/10.1016/j.jelechem.2014.09.038 Journal of Electroanalytical Chemistry Creative Commons Attribution-NonCommercial-NoDerivs License http://creativecommons.org/licenses/by-nc-nd/4.0/ application/pdf Elsevier arXiv |
| spellingShingle | Zeng, Yi Smith, Raymond Barrett Bai, Peng Bazant, Martin Z Simple formula for Marcus–Hush–Chidsey kinetics |
| title | Simple formula for Marcus–Hush–Chidsey kinetics |
| title_full | Simple formula for Marcus–Hush–Chidsey kinetics |
| title_fullStr | Simple formula for Marcus–Hush–Chidsey kinetics |
| title_full_unstemmed | Simple formula for Marcus–Hush–Chidsey kinetics |
| title_short | Simple formula for Marcus–Hush–Chidsey kinetics |
| title_sort | simple formula for marcus hush chidsey kinetics |
| url | http://hdl.handle.net/1721.1/107632 https://orcid.org/0000-0003-2421-6781 |
| work_keys_str_mv | AT zengyi simpleformulaformarcushushchidseykinetics AT smithraymondbarrett simpleformulaformarcushushchidseykinetics AT baipeng simpleformulaformarcushushchidseykinetics AT bazantmartinz simpleformulaformarcushushchidseykinetics |