@article{75848e0883fb4bc6abdfa427f195ed4d,
title = " Theoretical and computational investigations of geometrical, electronic and spin structures of the CaMn 4 O X (X = 5, 6) cluster in the Kok cycle S i (i = 0–3) of oxygen evolving complex of photosystem II ",
abstract = " The optimized geometries of the CaMn 4 O X (X = 5, 6) cluster in the oxygen evolving complex (OEC) of photosystem II (PSII) by large-scale quantum mechanics (QM) and molecular mechanics (MM) calculations are compared with recent serial femtosecond crystallography (SFX) results for the S i (i = 0–3) states. The valence states of four Mn ions by the QM/MM calculations are also examined in relation to the experimental results by the X-ray emission spectroscopy (XES) for the S i intermediates. Geometrical and valence structures of right-opened Mn-hydroxide, Mn-oxo and Mn-peroxide intermediates in the S 3 state are investigated in detail in relation to recent SFX and XES experiments for the S 3 state. Interplay between theory and experiment indicates that the Mn-oxo intermediate is a new possible candidate for the S 3 state. Implications of the computational results are discussed in relation to possible mechanisms of the oxygenoxygen bond formation for water oxidation in OEC of PSII. ",
author = "Kizashi Yamaguchi and Shusuke Yamanaka and Hiroshi Isobe and Mitsuo Shoji and Kouichi Miyagawa and Takahito Nakajima and Takashi Kawakami and Mitsutaka Okumura",
note = "Funding Information: One of the authors (K.Y.) thanks Dr. J. Kern for thorough discussions on the unpublished new SFX results for the S3 state by Berkeley group at the ePS-1 conference (Uppsala). K.Y. also thanks Prof. J.-R. Shen and Prof. N. Kamiya for helpful discussions on the experimental uncertainty of the XRD and SFX experiments. He also thanks for helpful comments and suggestions by the referees. This work has been supported by a Grants-in-Aid for Scientific Research on Innovation Areas No. 17H06433 (K.Y., H.I and M.S.) by the Ministry of Education, Culture, Sports, Science and Technology (MEXT) of Japan. Funding Information: Acknowledgements – One of the authors (K.Y.) thanks Dr. J. Kern for thorough discussions on the unpublished new SFX results for the S3 state by Berkeley group at the ePS-1 conference (Uppsala). K.Y. also thanks Prof. J.-R. Shen and Prof. N. Kamiya for helpful discussions on the experimental uncertainty of the XRD and SFX experiments. He also thanks for helpful comments and suggestions by the referees. This work has been supported by a Grants-in-Aid for Scientific Research on Innovation Areas No. 17H06433 (K.Y., H.I and M.S.) by the Ministry of Education, Culture, Sports, Science and Technology (MEXT) of Japan. Publisher Copyright: {\textcopyright} 2019 Scandinavian Plant Physiology Society",
year = "2019",
month = may,
doi = "10.1111/ppl.12960",
language = "English",
volume = "166",
pages = "44--59",
journal = "Physiologia Plantarum",
issn = "0031-9317",
publisher = "Wiley-Blackwell",
number = "1",
}