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Portrait of Tönu Pullerits; Photo: Kennet Ruona

Tönu Pullerits

Professor

Portrait of Tönu Pullerits; Photo: Kennet Ruona

Ultrafast formation of a carotenoid radical in LH2 antenna complexes of purple bacteria

Author

  • Tomas Polivka
  • Tönu Pullerits
  • H A Frank
  • R J Cogdell
  • Villy Sundström

Summary, in English

The SI-mediated carotenoid to BChl a energy-transfer pathway and carotenoid radical formation have been studied using femtosecond time-resolved transient absorption spectroscopy. A series of LH2 complexes (LH2 = light-harvesting complex 2) from Rhodobacter sphaeroides incorporating carotenoids neurosporene, spheroidene, and spheroidenone were used to explore the effect of conjugation length. The S, lifetimes of carotenoids in the LH2 complex are significantly shorter than in solution, resulting in efficiencies of the S-1-mediated energy transfer of 94%, 82%, and 76%, respectively. In addition to the S-1 decay, a low-amplitude component of similar to9 ps was revealed for all carotenoids in LH2 and assigned to the S* state. Besides energy transfer, excitation of the carotenoid S-2 state in LH2 complexes also leads to the formation of a carotenoid radical, and this pathway is also conjugation length dependent. The carotenoid radical is formed as a result of electron transfer between the carotenoid and B800 BChl a molecules. The yield of the radical formation is highest for neurosporene (10-15%), while a lower efficiency was observed for spheroidene (5-8%). For spheroidenone, no distinct radical signal was found, The precursor of the carotenoid radical is a charge-transfer state that is populated directly from the S-2 state. This charge-transfer state, which represents an excited state of the carotenoid-B800 complex, decays in 300 fs (neurosporene) or 400 fs (spheroidene) to form ground-state carotenoid cation and BChl anion. The charge-separated state has a lifetime of 2 ps (neurosporene) and 8 ps (spheroidene).

Department/s

  • Chemical Physics

Publishing year

2004

Language

English

Pages

15398-15407

Publication/Series

The Journal of Physical Chemistry Part B

Volume

108

Issue

39

Document type

Journal article

Publisher

The American Chemical Society (ACS)

Topic

  • Atom and Molecular Physics and Optics

Status

Published

ISBN/ISSN/Other

  • ISSN: 1520-5207