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Dynamics of electron transfer for a nonsuperexchange coherent mechanism. 1

Marcus, R. A. and Almeida, R. (1990) Dynamics of electron transfer for a nonsuperexchange coherent mechanism. 1. Journal of Physical Chemistry, 94 (7). pp. 2973-2977. ISSN 0022-3654. doi:10.1021/j100370a044.

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In addition to mechanisms such as superexchange and a chemical intermediate mechanism for electron transfer from a donor D* to an acceptor A via a molecular bridge B, a third possibility occurs when the BA electronic coupling is very strong and the D*B and D+B- states have energies moderately close to each other. This mechanism is discussed here. Like superexchange, it is a coherent one, in contrast to the chemical intermediate mechanism, where the transfer is sequential and incoherent. The dynamics of the mechanism are discussed, particularly the maximum population of "B-" and the question of whether an effective rate constant for its disappearance can be considerably larger than the maximum adiabatic rate constant. There are, as yet, no experimental data on the mechanism, though the synthesis of suitable D*BA's may permit its observation. In the treatment three collective nuclear coordinates are introduced, permitting independent reorganization energies for each reactive center. With certain approximations, namely, equal vibration frequencies and a nonadiabatic first step, the problem is reduced analytically to a one-coordinate one, which can be readily treated numerically. One rough but simple analytical result for the latter is also given.

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Marcus, R. A.0000-0001-6547-1469
Additional Information:© 1990 American Chemical Society. Received: August 15, 1989; In Final Form: October 13, 1989. Acknowledgment is made to the Office of Naval Research and to the donors of the Petroleum Research Fund, administered by the American Chemical Society, for the support of this research.
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Office of Naval Research (ONR)UNSPECIFIED
American Chemical Society Petroleum Research FundUNSPECIFIED
Issue or Number:7
Record Number:CaltechAUTHORS:20150422-135108860
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Official Citation:Dynamics of electron transfer for a nonsuperexchange coherent mechanism. 1 R. A. Marcus and R. Almeida The Journal of Physical Chemistry 1990 94 (7), 2973-2977 DOI: 10.1021/j100370a044
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:56881
Deposited By: Tony Diaz
Deposited On:22 Apr 2015 22:36
Last Modified:10 Nov 2021 21:05

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