Förster resonance energy transfer, absorption and emission spectra in multichromophoric systems. I. Full cumulant expansions and system-bath entanglement
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Cao_Forster resonance.pdf
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664.77 KB
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Author(s)
Ma, Jian
Cao, Jianshu
Date Issued
March 2015
Journal
Journal of Chemical Physics
Publisher
American Institute of Physics (AIP)
Citation
Ma, Jian, and Jianshu Cao. "Förster resonance energy transfer, absorption and emission spectra in multichromophoric systems. I. Full cumulant expansions and system-bath entanglement." Journal of Chemical Physics 142, 094106 (2015).
Version
Final published version
Abstract
We study the Förster resonant energy transfer rate, absorption and emission spectra in multichromophoric systems. The multichromophoric Förster theory (MCFT) is determined from an overlap integral of generalized matrices related to the donor’s emission and acceptor’s absorption spectra, which are obtained via a full 2nd-order cumulant expansion technique developed in this work. We calculate the spectra and MCFT rate for both localized and delocalized systems, and calibrate the analytical 2nd-order cumulant expansion with the exact stochastic path integral method. We present three essential findings: (i) The role of the initial entanglement between the donor and its bath is found to be crucial in both the emission spectrum and the MCFT rate. (ii) The absorption spectra obtained by the cumulant expansion method are nearly identical to the exact spectra for both localized and delocalized systems, even when the system-bath coupling is far from the perturbative regime. (iii) For the emission spectra, the cumulant expansion can give reliable results for localized systems, but fail to provide reliable spectra of the high-lying excited states of a delocalized system, when the system-bath coupling is large and the thermal energy is small. This paper also provides a simple golden-rule derivation of the MCFT, reviews existing methods, and motivates further developments in the subsequent papers.
MIT Department
Massachusetts Institute of Technology. Department of Chemistry
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DOI of Published Version
https://doi.org/10.1063/1.4908599
