Crossover from nonadiabatic to adiabatic electron transfer reactions: Multilevel blocking Monte Carlo simulations

The crossover from nonadiabatic to adiabatic electron transfer has been theoretically studied under a spin-boson model (dissipative two-state system) description. We present numerically exact data for the thermal transfer rate and the time-dependent occupation probabilities in largely unexplored reg...

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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 19.05.2002
Subjects
Adiabatic flow
Algorithms
Computer simulation
Crossovers
Data transfer (computers)
Decay rate
Electron transfer
Electron transfer reactions
Electrons
High temperature
Mathematical models
Monte Carlo simulation
Time dependence
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Summary:The crossover from nonadiabatic to adiabatic electron transfer has been theoretically studied under a spin-boson model (dissipative two-state system) description. We present numerically exact data for the thermal transfer rate and the time-dependent occupation probabilities in largely unexplored regions of parameter space, using real-time path-integral Monte Carlo simulations. The dynamical sign problem is relieved by employing a variant of the recently proposed multilevel blocking algorithm. We identify the crossover regime between nonadiabatic and adiabatic electron transfer, both in the classical (high-temperature) and the quantum (low-temperature) limit. The electron transfer dynamics displays rich behaviors, including multi-exponential decay and the breakdown of a rate description due to vibrational coherence.
ISSN:2331-8422
DOI:10.48550/arxiv.0205400