Multistate electron transfer dynamics in the condensed phase: Exact calculations from the reduced hierarchy equations of motion approach

Journal Article · Mon Jun 07 00:00:00 EDT 2010 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.3428674· OSTI ID:21559861

Tanaka, Midori; Tanimura, Yoshitaka ^[1]

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1. Department of Chemistry, Graduate School of Science, Kyoto University, Kyoto 606-8502 (Japan)

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.

• OSTI ID: 21559861
• Journal Information: Journal of Chemical Physics, Vol. 132, Issue 21; Other Information: DOI: 10.1063/1.3428674; (c) 2010 American Institute of Physics; ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

71 CLASSICAL AND QUANTUM MECHANICS
GENERAL PHYSICS
ACTIVATION ENERGY
ASYMMETRY
BROWNIAN MOVEMENT
CANONICAL TRANSFORMATIONS
CHARGE EXCHANGE
CORRELATION FUNCTIONS
DENSITY MATRIX
DISTRIBUTION
DISTURBANCES
ELECTRON TRANSFER
EQUATIONS OF MOTION
EVOLUTION
INTERMEDIATE STATE
OSCILLATORS
PERTURBATION THEORY
REACTION KINETICS
SIMULATION
VIBRATIONAL STATES
DIFFERENTIAL EQUATIONS
ELECTRONIC EQUIPMENT
ENERGY
ENERGY LEVELS
EQUATIONS
EQUIPMENT
EXCITED STATES
FUNCTIONS
KINETICS
MATRICES
PARTIAL DIFFERENTIAL EQUATIONS
TRANSFORMATIONS