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Title: Spectroscopic properties of photosystem II reaction center revisited

Abstract

Photosystem II (PSII) is the only biological system capable of splitting water to molecular oxygen. Its reaction center (RC) is responsible for the primary charge separation that drives the water oxidation reaction. In this work, we revisit the spectroscopic properties of the PSII RC using the complex time-dependent Redfield (ctR) theory for optical lineshapes [A. Gelzinis et al., J. Chem. Phys. 142, 154107 (2015)]. We obtain the PSII RC model parameters (site energies, disorder, and reorganization energies) from the fits of several spectra and then further validate the model by calculating additional independent spectra. We obtain good to excellent agreement between theory and calculations. We find that overall our model is similar to some of the previous asymmetric exciton models of the PSII RC. On the other hand, our model displays differences from previous work based on the modified Redfield theory. We extend the ctR theory to describe the Stark spectrum and use its fit to obtain the parameters of a single charge transfer state included in our model. Our results suggest that Chl$$+\atop{D1}$$Pheo$$-\atop{D1}$$ is most likely the primary charge transfer state, but that the Stark spectrum of the PSII RC is probably also influenced by other states.

Authors:
 [1];  [2];  [3];  [1]
  1. Vilnius Univ. (Lithuania); Center for Physical Sciences and Technology, Lilnius (Lithuania)
  2. Vilnius Univ. (Lithuania)
  3. Univ. of Michigan, Ann Arbor, MI (United States)
Publication Date:
Research Org.:
Univ. of Michigan, Ann Arbor, MI (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1535337
Alternate Identifier(s):
OSTI ID: 1400004
Grant/Contract Number:  
SC0016384
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 147; Journal Issue: 11; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
74 ATOMIC AND MOLECULAR PHYSICS; Chemistry; Physics

Citation Formats

Gelzinis, Andrius, Abramavicius, Darius, Ogilvie, Jennifer P., and Valkunas, Leonas. Spectroscopic properties of photosystem II reaction center revisited. United States: N. p., 2017. Web. doi:10.1063/1.4997527.
Gelzinis, Andrius, Abramavicius, Darius, Ogilvie, Jennifer P., & Valkunas, Leonas. Spectroscopic properties of photosystem II reaction center revisited. United States. doi:10.1063/1.4997527.
Gelzinis, Andrius, Abramavicius, Darius, Ogilvie, Jennifer P., and Valkunas, Leonas. Thu . "Spectroscopic properties of photosystem II reaction center revisited". United States. doi:10.1063/1.4997527. https://www.osti.gov/servlets/purl/1535337.
@article{osti_1535337,
title = {Spectroscopic properties of photosystem II reaction center revisited},
author = {Gelzinis, Andrius and Abramavicius, Darius and Ogilvie, Jennifer P. and Valkunas, Leonas},
abstractNote = {Photosystem II (PSII) is the only biological system capable of splitting water to molecular oxygen. Its reaction center (RC) is responsible for the primary charge separation that drives the water oxidation reaction. In this work, we revisit the spectroscopic properties of the PSII RC using the complex time-dependent Redfield (ctR) theory for optical lineshapes [A. Gelzinis et al., J. Chem. Phys. 142, 154107 (2015)]. We obtain the PSII RC model parameters (site energies, disorder, and reorganization energies) from the fits of several spectra and then further validate the model by calculating additional independent spectra. We obtain good to excellent agreement between theory and calculations. We find that overall our model is similar to some of the previous asymmetric exciton models of the PSII RC. On the other hand, our model displays differences from previous work based on the modified Redfield theory. We extend the ctR theory to describe the Stark spectrum and use its fit to obtain the parameters of a single charge transfer state included in our model. Our results suggest that Chl$+\atop{D1}$Pheo$-\atop{D1}$ is most likely the primary charge transfer state, but that the Stark spectrum of the PSII RC is probably also influenced by other states.},
doi = {10.1063/1.4997527},
journal = {Journal of Chemical Physics},
number = 11,
volume = 147,
place = {United States},
year = {2017},
month = {9}
}

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