2002/05/19 by L. Muehlbacher, Lothar Mühlbacher, R. Egger +1
Physics and Astronomy · #Advanced Chemical Physics Studies #Quantum and electron transport phenomena #Spectroscopy and Quantum Chemical Studies #cond-mat #physics.chem-ph
paper · pdf · doi:10.1063/1.1523014
published as J. Chem. Phys. 118, 179 (2003) · 15 pages, 14 figures submitted to the Journal of Chemical Physics
arxiv created 2002/05/19 · openalex publication_date 2002/12/19 · arxiv updated 2009/11/30 · openalex created_date 2016/06/24 · openalex updated_date 2026/07/28
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.