TY - CHAP
T1 - 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
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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U2 - 10.1007/978-3-642-32034-7_52
DO - 10.1007/978-3-642-32034-7_52
M3 - Chapter
AN - SCOPUS:85060674922
T3 - Advanced Topics in Science and Technology in China
SP - 250
EP - 254
BT - Advanced Topics in Science and Technology in China
PB - Springer
ER -