Electronic structure of the CaMn4O5 cluster in the PSII system refined to the 1.9 Å X-ray resolution. Possible mechanisms of photosynthetic water splitting

S. Yamanaka; K. Kanda; H. Isobe; K. Nakata; Y. Umena; K. Kawakami; J. R. Shen; N. Kamiya; M. Okumura; T. Takada; H. Nakamura; K. Yamaguchi

doi:10.1007/978-3-642-32034-7_52

Electronic structure of the CaMn₄O₅ cluster in the PSII system refined to the 1.9 Å X-ray resolution. Possible mechanisms of photosynthetic water splitting

S. Yamanaka, K. Kanda, H. Isobe, K. Nakata, Y. Umena, K. Kawakami, J. R. Shen, N. Kamiya, M. Okumura, T. Takada, H. Nakamura, K. Yamaguchi

Research Institute for Interdisciplinary Science

Research output: Chapter in Book/Report/Conference proceeding › Chapter

Abstract

Broken-symmetry (BS) UB3LYP calculations have been performed for the CaMn₄O₅ cluster (1) in the oxygen-evolving complex (OEC) of the PSII system refined to 1.9 Å resolution by Umena, Kawakami, Kamiya, Shen to elucidate its electronic structure that is crucial for consideration of possible mechanisms of photosynthetic water splitting. Our UB3LYP computations have elucidated the position of protonated oxygen of the CaMn(III)₂Mn(IV)₂O₄(OH) cluster (1a) at the S₁ stage of Kok cycle. Starting from the newly elucidated S₁ structure of 1a, we have calculated the electronic structure of proton and electron released CaMn(IV)₄O₅ cluster (1b) that mimics the S₄ stage of the cycle. The LUMOs of 1b are depicted for pictorial understanding of electrophilic oxygen sites that are responsible for nucleophilic attack of hydroxide anion (or water) for the O-O bond formation. Implications of present computational results are discussed in relation to possible mechanisms of photosynthetic water splitting.

Original language	English
Title of host publication	Advanced Topics in Science and Technology in China
Publisher	Springer
Pages	250-254
Number of pages	5
DOIs	https://doi.org/10.1007/978-3-642-32034-7_52
Publication status	Published - 2013

Publication series

Name	Advanced Topics in Science and Technology in China
ISSN (Print)	1995-6819
ISSN (Electronic)	1995-6827

Keywords

Ab initio DFT calculation
Electrophilic mechanism
LUMO
Protonated structure

ASJC Scopus subject areas

Chemical Engineering(all)
Engineering(all)
General

Access to Document

10.1007/978-3-642-32034-7_52

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Yamanaka, S., Kanda, K., Isobe, H., Nakata, K., Umena, Y., Kawakami, K., Shen, J. R., Kamiya, N., Okumura, M., Takada, T., Nakamura, H., & Yamaguchi, K. (2013). Electronic structure of the CaMn₄O₅ cluster in the PSII system refined to the 1.9 Å X-ray resolution. Possible mechanisms of photosynthetic water splitting. In Advanced Topics in Science and Technology in China (pp. 250-254). (Advanced Topics in Science and Technology in China). Springer. https://doi.org/10.1007/978-3-642-32034-7_52

Electronic structure of the CaMn₄O₅ cluster in the PSII system refined to the 1.9 Å X-ray resolution. Possible mechanisms of photosynthetic water splitting. / Yamanaka, S.; Kanda, K.; Isobe, H.; Nakata, K.; Umena, Y.; Kawakami, K.; Shen, J. R.; Kamiya, N.; Okumura, M.; Takada, T.; Nakamura, H.; Yamaguchi, K.

Advanced Topics in Science and Technology in China. Springer, 2013. p. 250-254 (Advanced Topics in Science and Technology in China).

Research output: Chapter in Book/Report/Conference proceeding › Chapter

Yamanaka, S, Kanda, K, Isobe, H, Nakata, K, Umena, Y, Kawakami, K, Shen, JR, Kamiya, N, Okumura, M, Takada, T, Nakamura, H & Yamaguchi, K 2013, Electronic structure of the CaMn₄O₅ cluster in the PSII system refined to the 1.9 Å X-ray resolution. Possible mechanisms of photosynthetic water splitting. in Advanced Topics in Science and Technology in China. Advanced Topics in Science and Technology in China, Springer, pp. 250-254. https://doi.org/10.1007/978-3-642-32034-7_52

Yamanaka S, Kanda K, Isobe H, Nakata K, Umena Y, Kawakami K et al. Electronic structure of the CaMn₄O₅ cluster in the PSII system refined to the 1.9 Å X-ray resolution. Possible mechanisms of photosynthetic water splitting. In Advanced Topics in Science and Technology in China. Springer. 2013. p. 250-254. (Advanced Topics in Science and Technology in China). https://doi.org/10.1007/978-3-642-32034-7_52

Yamanaka, S. ; Kanda, K. ; Isobe, H. ; Nakata, K. ; Umena, Y. ; Kawakami, K. ; Shen, J. R. ; Kamiya, N. ; Okumura, M. ; Takada, T. ; Nakamura, H. ; Yamaguchi, K. / Electronic structure of the CaMn₄O₅ cluster in the PSII system refined to the 1.9 Å X-ray resolution. Possible mechanisms of photosynthetic water splitting. Advanced Topics in Science and Technology in China. Springer, 2013. pp. 250-254 (Advanced Topics in Science and Technology in China).

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title = "Electronic structure of the CaMn4O5 cluster in the PSII system refined to the 1.9 {\AA} X-ray resolution. Possible mechanisms of photosynthetic water splitting",

abstract = "Broken-symmetry (BS) UB3LYP calculations have been performed for the CaMn4O5 cluster (1) in the oxygen-evolving complex (OEC) of the PSII system refined to 1.9 {\AA} resolution by Umena, Kawakami, Kamiya, Shen to elucidate its electronic structure that is crucial for consideration of possible mechanisms of photosynthetic water splitting. Our UB3LYP computations have elucidated the position of protonated oxygen of the CaMn(III)2Mn(IV)2O4(OH) cluster (1a) at the S1 stage of Kok cycle. Starting from the newly elucidated S1 structure of 1a, we have calculated the electronic structure of proton and electron released CaMn(IV)4O5 cluster (1b) that mimics the S4 stage of the cycle. The LUMOs of 1b are depicted for pictorial understanding of electrophilic oxygen sites that are responsible for nucleophilic attack of hydroxide anion (or water) for the O-O bond formation. Implications of present computational results are discussed in relation to possible mechanisms of photosynthetic water splitting.",

keywords = "Ab initio DFT calculation, Electrophilic mechanism, LUMO, Protonated structure",

author = "S. Yamanaka and K. Kanda and H. Isobe and K. Nakata and Y. Umena and K. Kawakami and Shen, {J. R.} and N. Kamiya and M. Okumura and T. Takada and H. Nakamura and K. Yamaguchi",

note = "Funding Information: This work has been supported by Grants-in-Aid for Scientific Research (Nos. 19750046, 19350070, 18350008) and for Research and Development of the Next-Generation Integrated Simulation of Living Matter, as a part of the Development and Use of the Next-Generation Supercomputer Project. Publisher Copyright: {\textcopyright} Zhejiang University Press, Hangzhou and Springer-Verlag Berlin Heidelberg 2013. Copyright: Copyright 2019 Elsevier B.V., All rights reserved.",

year = "2013",

doi = "10.1007/978-3-642-32034-7_52",

language = "English",

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AU - Yamanaka, S.

AU - Kanda, K.

AU - Isobe, H.

AU - Nakata, K.

AU - Umena, Y.

AU - Kawakami, K.

AU - Shen, J. R.

AU - Kamiya, N.

AU - Okumura, M.

AU - Takada, T.

AU - Nakamura, H.

AU - Yamaguchi, K.

N1 - Funding Information: This work has been supported by Grants-in-Aid for Scientific Research (Nos. 19750046, 19350070, 18350008) and for Research and Development of the Next-Generation Integrated Simulation of Living Matter, as a part of the Development and Use of the Next-Generation Supercomputer Project. Publisher Copyright: © Zhejiang University Press, Hangzhou and Springer-Verlag Berlin Heidelberg 2013. Copyright: Copyright 2019 Elsevier B.V., All rights reserved.

PY - 2013

Y1 - 2013

N2 - Broken-symmetry (BS) UB3LYP calculations have been performed for the CaMn4O5 cluster (1) in the oxygen-evolving complex (OEC) of the PSII system refined to 1.9 Å resolution by Umena, Kawakami, Kamiya, Shen to elucidate its electronic structure that is crucial for consideration of possible mechanisms of photosynthetic water splitting. Our UB3LYP computations have elucidated the position of protonated oxygen of the CaMn(III)2Mn(IV)2O4(OH) cluster (1a) at the S1 stage of Kok cycle. Starting from the newly elucidated S1 structure of 1a, we have calculated the electronic structure of proton and electron released CaMn(IV)4O5 cluster (1b) that mimics the S4 stage of the cycle. The LUMOs of 1b are depicted for pictorial understanding of electrophilic oxygen sites that are responsible for nucleophilic attack of hydroxide anion (or water) for the O-O bond formation. Implications of present computational results are discussed in relation to possible mechanisms of photosynthetic water splitting.

AB - Broken-symmetry (BS) UB3LYP calculations have been performed for the CaMn4O5 cluster (1) in the oxygen-evolving complex (OEC) of the PSII system refined to 1.9 Å resolution by Umena, Kawakami, Kamiya, Shen to elucidate its electronic structure that is crucial for consideration of possible mechanisms of photosynthetic water splitting. Our UB3LYP computations have elucidated the position of protonated oxygen of the CaMn(III)2Mn(IV)2O4(OH) cluster (1a) at the S1 stage of Kok cycle. Starting from the newly elucidated S1 structure of 1a, we have calculated the electronic structure of proton and electron released CaMn(IV)4O5 cluster (1b) that mimics the S4 stage of the cycle. The LUMOs of 1b are depicted for pictorial understanding of electrophilic oxygen sites that are responsible for nucleophilic attack of hydroxide anion (or water) for the O-O bond formation. Implications of present computational results are discussed in relation to possible mechanisms of photosynthetic water splitting.

KW - Ab initio DFT calculation

KW - Electrophilic mechanism

KW - LUMO

KW - Protonated structure

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