Electron transfer rates for asymmetric reactions

2003/06/11 by L. Muehlbacher, Lothar Mühlbacher, R. Egger +1 · 2 citations
Chemistry · Physics and Astronomy · #Advanced Chemical Physics Studies #Photochemistry and Electron Transfer Studies #Spectroscopy and Quantum Chemical Studies #cond-mat #physics.chem-ph

paper · pdf · doi:10.1016/j.chemphys.2003.08.021

published as Chem. Phys. 296, 193 (2004) · 13 pages, 4 figures, submitted to Chemical Physics Special Issue on the Spin-Boson Problem, ed. by H. Grabert and A. Nitzan

arxiv created 2003/06/11 · openalex publication_date 2003/10/27 · arxiv updated 2009/11/30 · openalex created_date 2016/06/24 · openalex updated_date 2026/07/28

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.

Citations

• Equilibrium Dynamics of the Dissipative Two-State System
• Exactc-Number Representation of Non-Markovian Quantum Dissipation
• Intramolecular long-distance electron transfer in radical anions. The effects of free energy and solvent on the reaction rates
• Dynamics of the dissipative two-state system

Cited by

• Electron transfer in donor-acceptor systems: Many-particle effects and influence of electronic correlations
• Non-oscillatory flux correlation functions for efficient nonadiabatic rate theory