Ultrafast excited state dynamics of fucoxanthin: excitation energy dependent intramolecular charge transfer dynamics
Autor: | Toshiyuki Kusumoto, Mitsuru Sugisaki, Naohiro Oka, Yoshiro Iinuma, Hideki Hashimoto, Daisuke Kosumi, Yuki Takaesu, Tomonori Taira, Masahiko Iha, Harry A. Frank, Ritsuko Fujii |
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Rok vydání: | 2011 |
Předmět: |
Cyclohexane
General Physics and Astronomy Molecular Dynamics Simulation Xanthophylls Photochemistry Polyene chemistry.chemical_compound chemistry Energy Transfer Excited state Intramolecular force Ultrafast laser spectroscopy Fucoxanthin Physical and Theoretical Chemistry Absorption (electromagnetic radiation) Excitation |
Zdroj: | Physical chemistry chemical physics : PCCP. 13(22) |
ISSN: | 1463-9084 |
Popis: | Carotenoids containing a carbonyl group in conjugation with their polyene backbone are naturally-occurring pigments in marine organisms and are essential to the photosynthetic light-harvesting function in aquatic algae. These carotenoids exhibit spectral characteristics attributed to an intramolecular charge transfer (ICT) state that arise in polar solvents due to the presence of the carbonyl group. Here, we report the spectroscopic properties of the carbonyl carotenoid fucoxanthin in polar (methanol) and nonpolar (cyclohexane) solvents studied by steady-state absorption and femtosecond pump-probe measurements. Transient absorption associated with the optically forbidden S(1) (2(1)A) state and/or the ICT state were observed following one-photon excitation to the optically allowed S(2) (1(1)B) state in methanol. The transient absorption measurements carried out in methanol showed that the ratio of the ICT-to-S(1) state formation increased with decreasing excitation energy. We also showed that the ICT character was clearly visible in the steady-state absorption in methanol based on a Franck-Condon analysis. The results suggest that two spectroscopic forms of fucoxanthin, blue and red, exist in the polar environment. |
Databáze: | OpenAIRE |
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