The ground state and excited state electronic properties of chlorophyll (Chl) a and Chl b in diethyl ether, acetone, and ethanol solutions are investigated using quantum mechanical and molecular mechanical calculations with density functional theory (DFT) and time-dependent DFT (TDDFT). Although the DFT/TDDFT methods are widely used, the electronic structures of molecules, especially large molecules, calculated with these methods are known to be strongly dependent on the functionals and the parameters used in the functionals. Here, we optimize the range-separated parameter, μ, of the CAM-B3LYP functional of Chl a and Chl b to reproduce the experimental excitation energy differences of these Chl molecules in solution. The optimal values of μ for Chl a and Chl b are smaller than the default value of μ and that for bacteriochlorophyll a, indicating the change in the electronic distribution, i.e., an increase in electron delocalization, within the molecule. We find that the electronic distribution of Chl b with an extra formyl group is different from that of Chl a. We also find that the polarity of the solution and hydrogen bond cause the decrease in the excitation energies and the increase in the widths of excitation energy distributions of Chl a and Chl b. The present results are expected to be useful for understanding the electronic properties of each pigment molecule in a local heterogeneous environment, which will play an important role in the excitation energy transfer in light-harvesting complex II.
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28 March 2022
Research Article|
March 28 2022
Excited states of chlorophyll a and b in solution by time-dependent density functional theory
Special Collection:
Photosynthetic Light-Harvesting and Energy Conversion
Zhe Zhu
;
Zhe Zhu
1
SOKENDAI (The Graduate University for Advanced Studies)
, Myodaiji, Okazaki, Aichi 444-8585, Japan
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Masahiro Higashi
;
Masahiro Higashi
2
Department of Molecular Engineering, Graduate School of Engineering, Kyoto University
, Kyoto daigaku-katsura, Nishikyo-ku, Kyoto 615-8510, Japan
3
JST, PRESTO
, 4-1-8 Honcho, Kawaguchi, Saitama 332-0012, Japan
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Shinji Saito
Shinji Saito
a)
1
SOKENDAI (The Graduate University for Advanced Studies)
, Myodaiji, Okazaki, Aichi 444-8585, Japan
4
Institute for Molecular Science
, Myodaiji, Okazaki, Aichi 444-8585, Japan
a)Author to whom correspondence should be addressed: [email protected]
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Zhe Zhu
1
Masahiro Higashi
2,3
Shinji Saito
1,4,a)
1
SOKENDAI (The Graduate University for Advanced Studies)
, Myodaiji, Okazaki, Aichi 444-8585, Japan
2
Department of Molecular Engineering, Graduate School of Engineering, Kyoto University
, Kyoto daigaku-katsura, Nishikyo-ku, Kyoto 615-8510, Japan
3
JST, PRESTO
, 4-1-8 Honcho, Kawaguchi, Saitama 332-0012, Japan
4
Institute for Molecular Science
, Myodaiji, Okazaki, Aichi 444-8585, Japan
a)Author to whom correspondence should be addressed: [email protected]
Note: This paper is part of the JCP Special Topic on Photosynthetic Light-Harvesting and Energy Conversion.
J. Chem. Phys. 156, 124111 (2022)
Article history
Received:
December 25 2021
Accepted:
March 02 2022
Citation
Zhe Zhu, Masahiro Higashi, Shinji Saito; Excited states of chlorophyll a and b in solution by time-dependent density functional theory. J. Chem. Phys. 28 March 2022; 156 (12): 124111. https://doi.org/10.1063/5.0083395
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