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Electron transfer rates in bridged molecular systems: a phenomenological approach to relaxation.

Journal Article · · J. Phys. Chem. A
DOI:https://doi.org/10.1021/jp970909c· OSTI ID:938196

A model for bridge-assisted, long-range electron transfer in a molecule interacting with a dissipative external bath is presented. The effects of the system-bath interaction are included phenomenologically in the evolution of the system density matrix as energy dephasings on the bridge sites. When the bridge dephasings are small, the steady state ET rate in this model is found to be the sum of two competing terms; the first is a McConnell-type rate arising from direct tunneling from donor to acceptor, and the second is a dephasing-dependent, length-independent scattering channel through the bridge sites. In the limit of large dephasings, an incoherent channel dominates the dynamics and leads to ET rates that can become only weakly dependent (k{sub ET} {proportional_to} 1/N) on the number of bridge sites in the system, for multisite bridges.

Research Organization:
Argonne National Laboratory (ANL)
Sponsoring Organization:
ER
DOE Contract Number:
AC02-06CH11357
OSTI ID:
938196
Report Number(s):
ANL/CHM/JA-28170
Journal Information:
J. Phys. Chem. A, Journal Name: J. Phys. Chem. A Journal Issue: 35 ; 1997 Vol. 101; ISSN 1089-5639; ISSN JPCAFH
Country of Publication:
United States
Language:
ENGLISH

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