4.5 Article

Energy Transfer Pathways in Light-Harvesting Complexes of Purple Bacteria as Revealed by Global Kinetic Analysis of Two-Dimensional Transient Spectra

Journal

JOURNAL OF PHYSICAL CHEMISTRY B
Volume 117, Issue 38, Pages 11349-11362

Publisher

AMER CHEMICAL SOC
DOI: 10.1021/jp403028x

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Funding

  1. Natural Sciences and Engineering Research Council of Canada
  2. DARPA (QuBE)
  3. United States Air Force Office of Scientific Research [FA9550-10-1-0260]
  4. BBSRC
  5. U.S. Department of Energy (DOE), Office of Basic Energy Sciences, as part of the Photosynthetic Antenna Research Center (PARC) Energy Frontier Research Center [DE-SC0001035]

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Excited state dynamics in LH2 complexes of two purple bacterial species were studied by broad-band two-dimensional electronic spectroscopy. The optical response was measured in the 500-600 nm spectral region on the 0-400 fs time scale. Global target analysis of two-dimensional (2D) transient spectra revealed the main energy transfer pathways between carotenoid S-2, 1B(u)(-) and S-1 states and bacteriochlorophyll Q(x) state. Global analysis ascertained the evolutionary and vibration-associated spectra, which also indicated the presence of a higher-lying vibrational level in the carotenoid S-1 state. The estimation of the spectral overlap between the 1B(u)(-) state and the Q(x) state indicated a significant contribution of the 1B(u)(-) state to the overall S-2-to-Q(x) excitation energy transfer.

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