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

V.I. Novoderezhkin, R. Croce, M.D. Wahadoszamen, I. Polukhina, E. Romero Mesa, R. van Grondelle

Research output: Contribution to JournalArticleAcademicpeer-review

Abstract

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.
Original languageEnglish
Pages (from-to)19368-19377
JournalPhysical Chemistry Chemical Physics - PCCP
Volume18
Issue number28
DOIs
Publication statusPublished - 2016

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charge transfer
excitons
chlorophylls
absorption spectra
fluorescence
spectral signatures
red shift
dichroism
excitation
antennas
dipoles

Cite this

@article{59173cd9029b460bb13d0cc819e42ccf,
title = "Mixing of exciton and charge-transfer states in light-harvesting complex Lhca4",
abstract = "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.",
author = "V.I. Novoderezhkin and R. Croce and M.D. Wahadoszamen and I. Polukhina and {Romero Mesa}, E. and {van Grondelle}, R.",
year = "2016",
doi = "10.1039/c6cp02225a",
language = "English",
volume = "18",
pages = "19368--19377",
journal = "Physical Chemistry Chemical Physics - PCCP",
issn = "1463-9076",
publisher = "The Royal Society of Chemistry",
number = "28",

}

Mixing of exciton and charge-transfer states in light-harvesting complex Lhca4. / Novoderezhkin, V.I.; Croce, R.; Wahadoszamen, M.D.; Polukhina, I.; Romero Mesa, E.; van Grondelle, R.

In: Physical Chemistry Chemical Physics - PCCP, Vol. 18, No. 28, 2016, p. 19368-19377.

Research output: Contribution to JournalArticleAcademicpeer-review

TY - JOUR

T1 - Mixing of exciton and charge-transfer states in light-harvesting complex Lhca4

AU - Novoderezhkin, V.I.

AU - Croce, R.

AU - Wahadoszamen, M.D.

AU - Polukhina, I.

AU - Romero Mesa, E.

AU - van Grondelle, R.

PY - 2016

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N2 - 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.

AB - 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.

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