Electron transfer rates for asymmetric reactions

Abstract

We use a numerically exact real-time path integral Monte Carlo scheme to compute electron transfer dynamics between two redox sites within a spin-boson approach. The case of asymmetric reactions is studied in detail in the least understood crossover region between nonadiabatic and adiabatic electron transfer. At intermediate-to-high temperature, we find good agreement with standard Marcus theory, provided dynamical recrossing effects are captured. The agreement with our data is practically perfect when temperature renormalization is allowed. At low temperature we find peculiar electron transfer kinetics in strongly asymmetric systems, characterized by rapid transient dynamics and backflow to the donor.

13 pages, 4 figures, submitted to Chemical Physics Special Issue on the Spin-Boson Problem, ed. by H. Grabert and A. Nitzan

References in corpus (8)

• Exact c-number Representation of Non-Markovian Quantum Dissipation
• Equilibrium dynamics of the dissipative two-state system
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• Ring-polymer instanton theory of electron transfer in the nonadiabatic limit
• Coherent-incoherent transition in the sub-Ohmic spin-boson model
• Refined Weak Coupling Limit: Coherence, Entanglement and Non-Markovianity
• Ground state properties of sub-Ohmic spin-boson model with simultaneous diagonal and off-diagonal coupling
• Symmetry and the critical phase of the two-bath spin-boson model: Ground-state properties
• Non-oscillatory flux correlation functions for efficient nonadiabatic rate theory
• Electron Transfer in Donor-Acceptor Systems: Many-Particle Effects and Influence of Electronic Correlations
• Impurity-Induced Environmental Quantum Phase Transitions in the Quadratic-Coupling Spin-Boson Model
• Equilibrium Dynamics of the Sub-Ohmic Spin-boson Model Under Bias
• Dynamical Spectral Function From Numerical Renormalization Group: A Full Excitation Approach