Journal
JOURNAL OF CHEMICAL PHYSICS
Volume 132, Issue 21, Pages -Publisher
AMER INST PHYSICS
DOI: 10.1063/1.3428674
Keywords
Brownian motion; charge exchange; quantum theory; reaction rate constants; vibrational states
Funding
- Japan Society for the Promotion of Science [B19350011]
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Multiple displaced oscillators coupled to an Ohmic heat bath are used to describe electron transfer (ET) in a dissipative environment. By performing a canonical transformation, the model is reduced to a multilevel system coupled to a heat bath with the Brownian spectral distribution. A reduced hierarchy equations of motion approach is introduced for numerically rigorous simulation of the dynamics of the three-level system with various oscillator configurations, for different nonadiabatic coupling strengths and damping rates, and at different temperatures. The time evolution of the reduced density matrix elements illustrates the interplay of coherences between the electronic and vibrational states. The ET reaction rates, defined as a flux-flux correlation function, are calculated using the linear response of the system to an external perturbation as a function of activation energy. The results exhibit an asymmetric inverted parabolic profile in a small activation regime due to the presence of the intermediate state between the reactant and product states and a slowly decaying profile in a large activation energy regime, which arises from the quantum coherent transitions. (C) 2010 American Institute of Physics. [doi: 10.1063/1.3428674]
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