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Quantum correction for electron transfer rates. Comparison of polarizable versus nonpolarizable descriptions of solvent

Song, Xueyu and Marcus, R. A. (1993) Quantum correction for electron transfer rates. Comparison of polarizable versus nonpolarizable descriptions of solvent. Journal of Chemical Physics, 99 (10). pp. 7768-7773. ISSN 0021-9606. http://resolver.caltech.edu/CaltechAUTHORS:SONjcp93

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Abstract

The electron transfer rate constant is treated using the spin-boson Hamiltonian model. The spectral density is related to the experimentally accessible data on the dielectric dispersion of the solvent, using a dielectric continuum approximation. On this basis the quantum correction for the ferrous–ferric electron transfer rate is found to be a factor 9.6. This value is smaller than the corresponding result (36) of Chandler and co-workers in their pioneering quantum simulation using a molecular model of the system [J. S. Bader, R. A. Kuharski, and D. Chandler, J. Chem. Phys. 93, 230 (1990)]. The likely reason for the difference lies in use of a rigid water molecular model in the simulation, since we find that other models for water in the literature which neglect the electronic and vibrational polarizability also give a large quantum effect. Such models are shown to overestimate the dielectric dispersion in one part of the quantum mechanically important region and to underestimate it in another part. It will be useful to explore a polarizable molecular model which reproduces the experimental dielectric response over the relevant part of the frequency spectrum.


Item Type:Article
Additional Information:Copyright © 1993 American Institute of Physics. Received 29 July 1993; accepted 13 August 1993. We would like to thank Dr. A.A. Stuchebrukhov and Dr. D. Chandler for insightful discussions. We are indebted to Dr. Joel Bader for providing the data file used in Fig. 2. It is a pleasure to acknowledge, too, the support of this research by the National Science Foundation and the Office of Naval Research. Arthur Amos Noyes Laboratory of Chemical Physics, Contribution No. 8833.
Subject Keywords:QUANTUM MECHANICS, CORRECTIONS, ELECTRON TRANSFER, SOLVENTS, POLARIZABILITY, SPIN, BOSONS, HAMILTONIANS, SPECTRAL DENSITY, DIELECTRIC PROPERTIES, AQUEOUS SOLUTIONS, MOLECULAR MODELS, ELECTRONIC STRUCTURE, VIBRATIONAL STATES, CHEMICAL REACTIONS, IRON IONS, EQUATIONS, COMPLEXES
Record Number:CaltechAUTHORS:SONjcp93
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:SONjcp93
Alternative URL:http://dx.doi.org/10.1063/1.465654
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:10900
Collection:CaltechAUTHORS
Deposited By: Archive Administrator
Deposited On:15 Jun 2008
Last Modified:26 Dec 2012 10:06

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