4.5 Article

Davydov Splitting of Excitons in Cyclic Bacteriochlorophyll a Nanoaggregates of Bacterial Light-Harvesting Complexes between 4.5 and 263 K

Journal

CHEMPHYSCHEM
Volume 12, Issue 3, Pages 634-644

Publisher

WILEY-V C H VERLAG GMBH
DOI: 10.1002/cphc.201000913

Keywords

excitons; fluorescence; nano-aggregates; photochemistry; photosynthetic light harvesting

Funding

  1. Estonian Science Foundation [8674]
  2. Estonian Ministry of Education and Science [SF0180055s07]
  3. Research Council of Lithuania [MIP-110/2010]

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The nature of electronic excitations created by photon absorption in the cyclic B850 aggregates of 18 bacteriochlorophyll molecules of LH2 antenna complexes of photosynthetic bacteria is studied over a broad temperature range using absorption, fluorescence, and fluorescence anisotropy spectra. The latter technique has been proved to be suitable for revealing the hidden structure of excitons in inhomogeneously broadened spectra of cyclic aggregates. A theoretical model that accounts for differences of absorbing excitons in undeformed and emitting exciton polarons in deformed antenna lattices is also developed. Only a slight decrease of the exciton bandwidth and exciton coupling energy with temperature is observed. Survival of excitons in the whole temperature span from cryogenic to nearly ambient temperatures strongly suggests that collective, coherent electronic excitations might play a role in the functional light-harvesting process taking place at physiological temperatures.

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