Mixing of exciton and charge-transfer states in light-harvesting complex Lhca4

文献情報

出版日 2016-06-23

DOI 10.1039/C6CP02225A

インパクトファクター 3.676

著者

Vladimir I. Novoderezhkin, Roberta Croce, Iryna Polukhina, Elisabet Romero, Rienk van Grondelle

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要旨

Lhca4 is one of the peripheral antennae of higher plant photosystem I and it is characterized by the presence of chlorophyll a with absorption and emission bands around 30 nm red-shifted compared to those of the other chlorophylls associated with plant complexes. In this work we have investigated the origin of this red shift by using the recent structure of Lhca4 (Qin et al., Science, 2015, 348, 989) to build an exciton model that includes a charge-transfer (CT) state mixed with the excited-state manifold. A simultaneous quantitative fit of absorption, linear dichroism, fluorescence, and Stark absorption spectra of the wild-type Lhca4 and NH mutant (where the sites involved in CT are affected) enables us to determine the origin of the CT state and explore its spectral signatures. A huge borrowing of dipole strength by the CT, accompanied by anomalous broadening and red-shifting of the fluorescence as well as dramatic changes in the Stark spectrum, can be accounted for by a model implying an exciton-type mixing between excited states and CT states.

掲載誌

Physical Chemistry Chemical Physics

CiteScore: 5.5

自己引用率: 10.3%

年間論文数: 3036

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