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Kinetics and thermodynamics of electron transfer in Debye solvents: an analytical and nonperturbative reduced density matrix theory.

Han P, Xu RX, Li B, Xu J, Cui P, Mo Y, Yan Y

State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China.

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.

Published 14 June 2006 in J Phys Chem B Condens Matter Mater Surf Interfaces Biophys, 110(23): 11438-43.
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