Journal
JOURNAL OF CHEMICAL PHYSICS
Volume 125, Issue 11, Pages -Publisher
AMER INST PHYSICS
DOI: 10.1063/1.2353148
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Effects of anharmonic bridge vibrations on electronic tunneling in donor-bridge-acceptor complexes are studied using a model of anharmonic bridge vibration coupled nonlinearly to an electronic degree of freedom. An anharmonicity parameter is introduced, enabling to reproduce the standard harmonic model with linear coupling as a limiting case. The frequency of electronic tunneling oscillations between the donor and acceptor sites is shown to be sensitive to the nuclear anharmonicity, where stretching and compression modes have an opposite effect on the electronic frequency. This phenomenon, that cannot be accounted for within the harmonic approximation, is analyzed and explained. (c) 2006 American Institute of Physics.
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