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Theory of highly exothermic electron transfer reactions

Marcus, R. A. and Siders, Paul (1982) Theory of highly exothermic electron transfer reactions. Journal of Physical Chemistry, 86 (5). pp. 622-630. ISSN 0022-3654. https://resolver.caltech.edu/CaltechAUTHORS:20150626-132435823

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Abstract

The theory of highly exothermic homogeneous outer-sphere electron transfer reactions is discussed for transfers occurring over a range of distances. A finite rate of diffusion of reactants and their long-range force are treated by solving the diffusion equation numerically for the reactant pair distribution function. Steady-state solutions for the bimolecular rate constant are compared with experimental data as well as with our recent approximate analytic solution, which is found to agree in the present case. On the basis of short-time solutions, it is proposed that experiments which measure electron transfer rates at short times following the onset of reaction improve the possibility of observing the inverted effect in bimolecular systems. The chance of seeing it in linked systems (unimolecular reactions) is even greater. The relation between the prediction of an “inverted region” in the rate constant vs. ΔG° plot and the existence of a maximum in charge transfer spectral plots of intensity vs. absorption frequency is pointed out.


Item Type:Article
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http://dx.doi.org/10.1021/j100394a009 DOIArticle
http://pubs.acs.org/doi/abs/10.1021/j100394a009PublisherArticle
ORCID:
AuthorORCID
Marcus, R. A.0000-0001-6547-1469
Additional Information:© 1982 American Chemical Society. Received: August 6, 1981; In Final Form: October 21, 1981. It is a pleasure to acknowledge support of this research by a grant from the National Science Foundation. The calculations reported in this paper made use of the Dreyfus-NSF theoretical chemistry computer which was funded through grants from the Camille and Henry Dreyfus Foundation, the National Science Foundation, and the Sloan Fund of the California Institute of Technology.
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NSFUNSPECIFIED
Camille and Henry Dreyfus FoundationUNSPECIFIED
Sloan Fund, CaltechUNSPECIFIED
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Caltech Arthur Amos Noyes Laboratory of Chemical Physics6502
Issue or Number:5
Record Number:CaltechAUTHORS:20150626-132435823
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20150626-132435823
Official Citation:Theory of highly exothermic electron transfer reactions R. A. Marcus and Paul Siders The Journal of Physical Chemistry 1982 86 (5), 622-630 DOI: 10.1021/j100394a009
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:58642
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:27 Jun 2015 17:46
Last Modified:22 Nov 2019 09:58

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