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Kinetics and Thermodynamics of Electron Transfer in Debye Solvents: An Analytical and Nonperturbative Reduced Density Matrix Theory

Ping Han,^†^§ Rui-Xue Xu,*^‡^§ Baiqing Li,^‡^§ Jian Xu,^‡ Ping Cui,^‡^§ Yan Mo,^§ and YiJing Yan*^†^‡^§

State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China, Hefei National Laboratory for Physical Sciences at the Microscale, University of Science and Technology of China, Hefei 230026, China, and Department of Chemistry, Hong Kong University of Science and Technology, Kowloon, Hong Kong

J. Phys. Chem. B, 2006, 110 (23), pp 11438–11443

DOI: 10.1021/jp062133y

Publication Date (Web): May 20, 2006

†

Chinese Academy of Sciences.

Hong Kong University of Science and Technology.

E-mail addresses: rxxu@ustc.edu.cn (R.-X.X.); yyan@ust.hk (Y.J.Y.).

‡

University of Science and Technology of China.

Abstract

A nonperturbative electron transfer rate theory is developed on the basis of reduced density matrix dynamics, which can be evaluated readily for the Debye solvent model without further approximation. Not only does it recover for reaction rates the celebrated Marcus' inversion and Kramers' turnover behaviors, but the present theory also predicts reaction thermodynamics, such as equilibrium Gibbs free energy and entropy, some interesting solvent-dependent features that are calling for experimental verification. Moreover, a continued fraction Green's function formalism is also constructed, which can be used together with the Dyson equation technique for efficient evaluation of nonperturbative reduced density matrix dynamics.

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