Coherent versus incoherent excitation energy transfer in molecular systems
Journal
Journal of Chemical Physics
Journal Volume
137
Journal Issue
16
Date Issued
2012
Author(s)
Chang, Hung-Tzu
Abstract
We investigate the Markovian limit of a polaronic quantum master equation for coherent resonance energy transfer proposed recently by Jang et al. [J. Chem. Phys. 129, 101104 (2008)]. An expression for the rate of excitation energy transfer (EET) is derived and shown to exhibit both coherent and incoherent contributions. We then apply this theory to calculated EET rates for model dimer systems, and demonstrate that the small-polaron approach predicts a variety of dynamical behaviors. Notably, the results indicate that the EET dynamical behaviors can be understood by the interplay between noise-assisted EET and dynamical localization, while both are well captured by the polaron theory. Finally, we investigate bath correlation effects on the rate of EET and show that bath correlations (or anti-correlations) can either enhance or suppress EET rate depending on the strength of individual system-bath couplings. In summary, we introduce the small-polaron approach as an intuitive physical framework to consolidate our understanding of EET dynamics in the condensed phase.
SDGs
Type
journal article