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Title: Impact of environmentally induced fluctuations on quantum mechanically mixed electronic and vibrational pigment states in photosynthetic energy transfer and 2D electronic spectra

Journal Article · · Journal of Chemical Physics
DOI:https://doi.org/10.1063/1.4914302· OSTI ID:1407280
 [1]; ORCiD logo [2];  [1]
  1. National Inst. of Natural Sciences, Okazaki (Japan). Inst. for Molecular Science
  2. Univ. of California, Berkeley, CA (United States). Dept. of Chemistry

Recently, nuclear vibrational contribution signatures in two-dimensional (2D) electronic spectroscopy have attracted considerable interest, in particular as regards interpretation of the oscillatory transients observed in light-harvesting complexes. These transients have dephasing times that persist for much longer than theoretically predicted electronic coherence lifetime. As a plausible explanation for this long-lived spectral beating in 2D electronic spectra, quantum-mechanically mixed electronic and vibrational states (vibronic excitons) were proposed by Christensson et al. [J. Phys. Chem. B 116, 7449 (2012)] and have since been explored. Here in this work, we address a dimer which produces little beating of electronic origin in the absence of vibronic contributions, and examine the impact of protein-induced fluctuations upon electronic-vibrational quantum mixtures by calculating the electronic energy transfer dynamics and 2D electronic spectra in a numerically accurate manner. It is found that, at cryogenic temperatures, the electronic-vibrational quantum mixtures are rather robust, even under the influence of the fluctuations and despite the small Huang-Rhys factors of the Franck-Condon active vibrational modes. This results in long-lasting beating behavior of vibrational origin in the 2D electronic spectra. At physiological temperatures, however, the fluctuations eradicate the mixing, and hence, the beating in the 2D spectra disappears. Further, it is demonstrated that such electronic-vibrational quantum mixtures do not necessarily play a significant role in electronic energy transfer dynamics, despite contributing to the enhancement of long-lived quantum beating in 2D electronic spectra, contrary to speculations in recent publications.

Research Organization:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
AC02-05CH11231; 25708003
OSTI ID:
1407280
Journal Information:
Journal of Chemical Physics, Vol. 142, Issue 21; ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 76 works
Citation information provided by
Web of Science

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Coherent wavepackets in the Fenna–Matthews–Olson complex are robust to excitonic-structure perturbations caused by mutagenesis journal January 2018
Supramolecular photochemistry applied to artificial photosynthesis and molecular logic devices journal January 2015
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Elucidation of reactive wavepackets by two-dimensional resonance Raman spectroscopy journal September 2015
A method for the direct measurement of electronic site populations in a molecular aggregate using two-dimensional electronic-vibrational spectroscopy journal September 2015
Energy transfer in structured and unstructured environments: Master equations beyond the Born-Markov approximations journal January 2016
Effects of Herzberg–Teller vibronic coupling on coherent excitation energy transfer journal November 2016
Signatures of vibronic coupling in two-dimensional electronic-vibrational and vibrational-electronic spectroscopies journal September 2017
Electronic energy transfer through non-adiabatic vibrational-electronic resonance. II. 1D spectra for a dimer journal February 2018
Impact of undamped and damped intramolecular vibrations on the efficiency of photosynthetic exciton energy transfer journal April 2018
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