Effects of anharmonicity on diffusive-controlled symmetric electron transfer rates: From the weak to the strong electronic coupling regions
- Department of Chemical Physics, University of Science and Technology of China, Hefei 230026 (China)
- State Key Laboratory of Physical Chemistry of Solid Surfaces and Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Fujian 361005 (China)
The approach for the diffusive-controlled electron transfer rates [W. Zhu and Y. Zhao, J. Chem. Phys. 126, 184105 (2007)], which is modeled after the Sumi-Marcus theory, is applied to symmetric electron-transfer reactions in a solvent environment with anharmonic potential functions. The electron-transfer rates are evaluated using the quantum R-matrix theory for dealing with the intramolecular vibrational motions and imaginary-time split operator technique for solving the diffusive equations, thereby taking explicit account of the weak-to-strong electronic couplings. The effect of anharmonicity for both the solvent and intramolecular vibrational degrees of freedom are investigated. It is found that the anharmonicity of the intramolecular modes always enhances the rate while the solvent anharmonicity decreases the rate, compared with the harmonic modes. The possible mechanisms have been clarified.
- OSTI ID:
- 21254877
- Journal Information:
- Journal of Chemical Physics, Vol. 129, Issue 18; Other Information: DOI: 10.1063/1.3012357; (c) 2008 American Institute of Physics; Country of input: International Atomic Energy Agency (IAEA); ISSN 0021-9606
- Country of Publication:
- United States
- Language:
- English
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