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Dynamical effects in electron transfer reactions

Sumi, H. and Marcus, R. A. (1986) Dynamical effects in electron transfer reactions. Journal of Chemical Physics, 84 (9). pp. 4894-4914. ISSN 0021-9606. doi:10.1063/1.449978.

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A theoretical treatment is given for the effect of intramolecular vibrational and diffusive solvent orientational motions on the rate of electron transfer reactions. Four limiting cases are considered for the two-electronic state problem: slow reaction, wide and narrow reaction window, and nondiffusing limits. With the aid of a decoupling approximation, an expression is derived for the reaction rate which reduces to the appropriate expression for each limiting case when the latter is approached. Under certain conditions the time dependence of the survival probability is multiexponential rather than single exponential. Because of this behavior two average survival times are defined and expressions for each are obtained. Experimental data are considered with the present treatment in mind. One feature of the present work is a more general analysis for the case that both vibrational and solvent diffusive motion contribute to the activation process. The relation to previous works in the literature is described.

Item Type:Article
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Marcus, R. A.0000-0001-6547-1469
Additional Information:Copyright © 1986 American Institute of Physics. Received 29 July 1985; accepted 26 December 1985. One of the authors (H.S.) would like to thank Professor Marcus' group and Professor McKoy's group for the hospitality given him during his stay at California Institute of Technology. The support of this research by a grant from the Ministry of Education of Japan (to H.S.) and from the National Science Foundation (to R.A.M.) is gratefully acknowledged. Arthur Amos Noyes Laboratory of Chemical Physics, Contribution No. 7253.
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Ministry of Education (Japan)UNSPECIFIED
National Science FoundationUNSPECIFIED
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Arthur Amos Noyes Laboratory of Chemical Physics7253
Issue or Number:9
Record Number:CaltechAUTHORS:SUMjcp86b
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Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:12165
Deposited By: Archive Administrator
Deposited On:27 Oct 2008 23:54
Last Modified:08 Nov 2021 22:26

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