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Issue 15, 2003
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Chlorophyll fluorescence quenching by xanthophylls

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Abstract

The interactions of the xanthophylls zeaxanthin, antheraxanthin and violaxanthin with chlorophyll, which are relevant for the chlorophyll fluorescence quenching in the non-photochemical quenching (NPQ) process in green plants, are investigated by means of quantum chemical methods. In particular, we use a hybrid approach consisting of time-dependent density-functional theory (TDDFT) and configuration interactions singles (CIS), since present-day TDDFT alone fails in describing relevant long-range charge-transfer states. Calculation of the energetically lowest excited states of a zea–chl dimer along the intermolecular distance coordinate shows that two mechanisms for chlorophyll fluorescence quenching are possible: quenching via excitation-energy transfer and electron-transfer quenching. The relevance of both mechanisms is discussed by comparison to corresponding anthera–chl and vio–chl dimers and the dependence of the mechanism on the geometrical arrangement of the dimers is illuminated. It is pointed out that the typical absorption band of the zeaxanthin radical cation can be used to experimentally determine whether a zea–chl dimer is present during NPQ.

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Publication details

The article was received on 02 May 2003, accepted on 18 Jun 2003 and first published on 04 Jul 2003


Article type: Paper
DOI: 10.1039/B304944B
Citation: Phys. Chem. Chem. Phys., 2003,5, 3247-3256
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    Chlorophyll fluorescence quenching by xanthophylls

    A. Dreuw, G. R. Fleming and M. Head-Gordon, Phys. Chem. Chem. Phys., 2003, 5, 3247
    DOI: 10.1039/B304944B

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