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Linear response in theory of electron transfer reactions as an alternative to the molecular harmonic oscillator model

Georgievskii, Yuri and Hsu, Chao-Ping and Marcus, R. A. (1999) Linear response in theory of electron transfer reactions as an alternative to the molecular harmonic oscillator model. Journal of Chemical Physics, 110 (11). pp. 5307-5317. ISSN 0021-9606.

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The effect of solvent fluctuations on the rate of electron transfer reactions is considered using linear response theory and a second-order cumulant expansion. An expression is obtained for the rate constant in terms of the dielectric response function of the solvent. It is shown thereby that this expression, which is usually derived using a molecular harmonic oscillator ("spin-boson") model, is valid not only for approximately harmonic systems such as solids but also for strongly molecularly anharmonic systems such as polar solvents. The derivation is a relatively simple alternative to one based on quantum field theoretic techniques. The effect of system inhomogeneity due to the presence of the solute molecule is also now included. An expression is given generalizing to frequency space and quantum mechanically the analogue of an electrostatic result relating the reorganization free energy to the free energy difference of two hypothetical systems [J. Chem. Phys. 39, 1734 (1963)]. The latter expression has been useful in adapting specific electrostatic models in the literature to electron transfer problems, and the present extension can be expected to have a similar utility.

Item Type:Article
Additional Information:©1999 American Institute of Physics. (Received 21 October 1998; accepted 16 December 1998) It is a pleasure to acknowledge the support of the National Science Foundation and the Office of Naval Research. One of us (Y.G.) would like to acknowledge the support of the James W. Glanville Postdoctoral Scholarship in Chemistry at Caltech. We would also like to thank Shaul Mukamel, Bruce Berne, and David Chandler for helpful comments.
Subject Keywords:charge exchange; free energy; chemical reactions; reaction rate constants
Record Number:CaltechAUTHORS:GEOjcp99
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Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:2142
Deposited By: Archive Administrator
Deposited On:11 Mar 2006
Last Modified:26 Dec 2012 08:47

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