Förster resonance energy transfer, absorption and emission spectra in multichromophoric systems. II. Hybrid cumulant expansion
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Cao_Forster resonanceII.pdf
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810.62 KB
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Author(s)
Ma, Jian
Moix, Jeremy
Cao, Jianshu
Date Issued
March 2015
Journal
Journal of Chemical Physics
Publisher
American Institute of Physics (AIP)
Citation
Ma, Jian; Moix, Jeremy and Cao, Jianshu. “Förster Resonance Energy Transfer, Absorption and Emission Spectra in Multichromophoric Systems. II. Hybrid Cumulant Expansion.” Journal of Chemical Physics 142, 9 (March 2015): 094107 © 2015 AIP Publishing LLC
Version
Final published version
Abstract
We develop a hybrid cumulant expansion method to account for the system-bath entanglement in the emission spectrum in the multi-chromophoric Förster transfer rate. In traditional perturbative treatments, the emission spectrum is usually expanded with respect to the system-bath coupling term in both real and imaginary time. This perturbative treatment gives a reliable absorption spectrum, where the bath is Gaussian and only the real-time expansion is involved. For the emission spectrum, the initial state is an entangled state of the system plus bath. Traditional perturbative methods are problematic when the excitations are delocalized and the energy gap is larger than the thermal energy, since the second-order expansion cannot predict the displacement of the bath. In the present method, the real-time dynamics is carried out by using the 2nd-order cumulant expansion method, while the displacement of the bath is treated more accurately by utilizing the exact reduced density matrix of the system. In a sense, the hybrid cumulant expansion is based on a generalized version of linear response theory with entangled initial states.
MIT Department
Massachusetts Institute of Technology. Department of Chemistry
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DOI of Published Version
https://doi.org/10.1063/1.4908600
