Electron transfer rates for asymmetric reactions

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...

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Bibliographic Details
Published inarXiv.org
Main Authors Muehlbacher, L, Egger, R
Format Paper
LanguageEnglish
Published Ithaca Cornell University Library, arXiv.org 11.06.2003
Subjects
Asymmetry
Computer simulation
Crossovers
Electron transfer
Electrons
High temperature
Reaction kinetics
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Summary: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.
ISSN:2331-8422
DOI:10.48550/arxiv.0306269