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Reflections on electron transfer theory

Marcus, Rudolph A. (2020) Reflections on electron transfer theory. Journal of Chemical Physics, 153 (21). Art. No. 210401. ISSN 0021-9606. https://resolver.caltech.edu/CaltechAUTHORS:20201207-153231500

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Abstract

Some of the early history leading to the 1956 The Journal of Chemical Physics article on a theory of electron transfer reactions is described. In the development of electron transfer theory in 1956, the simplicity of the final equation for the free energy barrier, after a lengthy and complex derivation, came to me as a surprise. It was indeed a “Eureka” moment, and I give some of its history here. The theory developed via a rather circuitous route, beginning with a question from a graduate student in a class on statistical mechanics that I taught at Brooklyn Poly. The question was whether a certain model (the Ising model) involving nearest neighbor interactions could be applied to shielded charges along a polymeric chain, a polyelectrolyte. His interest was in applying the theory to experimental data he was obtaining in the laboratory. The answer was yes, and I became interested more generally in the electrostatic properties of polyelectrolytes and in the several seemingly different ways of calculating their electrostatic free energy. To extend my background in electrostatics and treat this topic in a more fundamental way I researched every book on electrostatics/electromagnetic theory in the Brooklyn Poly library and found one that provided physical insight into the various concepts. After writing a pair of articles on polyelectrolytes, I then wondered what to do next. I had long decided that applying a theory I derived in 1952, later known as Rice–Ramsperger–Kassel–Marcus (RRKM) theory, was not a desirable option. There were almost no relevant experimental data on unimolecular reactions or bimolecular recombination reactions at the time. Extensive data, laboratory and computational, for testing the theory were to come later in the 1960s and subsequent decades.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://doi.org/10.1063/5.0035434DOIArticle
ORCID:
AuthorORCID
Marcus, Rudolph A.0000-0001-6547-1469
Additional Information:© 2020 Published under license by AIP Publishing. Submitted: 28 October 2020; Accepted: 12 November 2020; Published Online: 2 December 2020. This paper is part of the JCP Special Topic on 65 Years of Electron Transfer. The author is pleased to acknowledge the support of his research from the Office of Naval Research and the Army Research Office.
Funders:
Funding AgencyGrant Number
Office of Naval Research (ONR)UNSPECIFIED
Army Research Office (ARO)UNSPECIFIED
Issue or Number:21
Record Number:CaltechAUTHORS:20201207-153231500
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20201207-153231500
Official Citation:Reflections on electron transfer theory; Rudolph A. Marcus, The Journal of Chemical Physics 153:21: DOI: 10.1063/5.0035434
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:106954
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:07 Dec 2020 23:49
Last Modified:07 Dec 2020 23:49

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