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Title: Influences of Quantum Mechanically Mixed Electronic and Vibrational Pigment States in 2D Electronic Spectra of Photosynthetic Systems: Strong Electronic Coupling Cases

In 2D electronic spectroscopy studies, long-lived quantum beats have recently been observed in photosynthetic systems, and several theoretical studies have suggested that the beats are produced by quantum mechanically mixed electronic and vibrational states. Concerning the electronic-vibrational quantum mixtures, the impact of protein-induced fluctuations was examined by calculating the 2D electronic spectra of a weakly coupled dimer with the Franck-Condon active vibrational modes in the resonant condition. This analysis demonstrated that quantum mixtures of the vibronic resonance are rather robust under the influence of the fluctuations at cryogenic temperatures, whereas the mixtures are eradicated by the fluctuations at physiological temperatures. However, this conclusion cannot be generalized because the magnitude of the coupling inducing the quantum mixtures is proportional to the inter-pigment electronic coupling. In this paper, we explore the impact of the fluctuations on electronic-vibrational quantum mixtures in a strongly coupled dimer with an off-resonant vibrational mode. Toward this end, we calculate energy transfer dynamics and 2D electronic spectra of a model dimer that corresponds to the most strongly coupled bacteriochlorophyll molecules in the Fenna-Matthews-Olson complex in a numerically accurate manner. The quantum mixtures are found to be robust under the exposure of protein-induced fluctuations at cryogenic temperatures, irrespective ofmore » the resonance. At 300 K, however, the quantum mixing is disturbed more strongly by the fluctuations, and therefore, the beats in the 2D spectra become obscure even in a strongly coupled dimer with a resonant vibrational mode. Further, the overall behaviors of the energy transfer dynamics are demonstrated to be dominated by the environment and coupling between the 0 0 vibronic transitions as long as the Huang-Rhys factor of the vibrational mode is small. Finally, the 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 the 2D spectra.« less
 [1] ;  [2] ;  [1]
  1. National Inst. of Natural Sciences (NINS), Okazaki (Japan). Inst. for Molecular Science
  2. Univ. of California, Berkeley, CA (United States). Dept. of Chemistry; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Physical Biosciences Division
Publication Date:
Grant/Contract Number:
AC02-05CH11231; 25708003
Accepted Manuscript
Journal Name:
Journal of the Chinese Chemical Society
Additional Journal Information:
Journal Volume: 63; Journal Issue: 1; Journal ID: ISSN 0009-4536
Research Org:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); Japan Society for the Promotion of Science (JSPS) (Japan)
Contributing Orgs:
Univ. of California, Berkeley, CA (United States)
Country of Publication:
United States
74 ATOMIC AND MOLECULAR PHYSICS; photosynthetic energy transfer; dissipative quantum dynamics; 2D electronic spectra
OSTI Identifier: