Spin, Valence, and Structural Isomerism in the S<sub>3</sub> State of the Oxygen-Evolving Complex of Photosystem II as a Manifestation of Multimetallic Cooperativity
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- Hiroshi Isobe
- Research Institute for Interdisciplinary Science, Okayama University, Okayama 700-8530, Japan
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- Mitsuo Shoji
- Center for Computational Science, University of Tsukuba, Tsukuba, Ibaraki 305-8577, Japan
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- Takayoshi Suzuki
- Research Institute for Interdisciplinary Science, Okayama University, Okayama 700-8530, Japan
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- Jian-Ren Shen
- Research Institute for Interdisciplinary Science, Okayama University, Okayama 700-8530, Japan
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- Kizashi Yamaguchi
- Institute for NanoScience Design, Osaka University, Toyonaka, Osaka 560-0043, Japan
書誌事項
- 公開日
- 2019-03-11
- 資源種別
- journal article
- 権利情報
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- https://doi.org/10.15223/policy-029
- https://doi.org/10.15223/policy-037
- https://doi.org/10.15223/policy-045
- DOI
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- 10.1021/acs.jctc.8b01055
- 公開者
- American Chemical Society (ACS)
この論文をさがす
説明
Photosynthetic water oxidation is catalyzed by a Mn4CaO5-cluster in photosystem II through an S-state cycle. Understanding the roles of heterogeneity in each S-state, as identified recently by the EPR spectroscopy, is very important to gain a complete description of the catalytic mechanism. We performed herein hybrid DFT calculations within the broken-symmetry formalism and associated analyses of Heisenberg spin models to study the electronic and spin structures of various isomeric structural motifs (hydroxo–oxo, oxyl–oxo, peroxo, and superoxo species) in the S3 state. Our extensive study reveals several factors that affect the spin ground state: (1) (formal) Mn oxidation state; (2) metal–ligand covalency; (3) coordination geometry; and (4) structural change of the Mn cluster induced by alternations in Mn···Mn distances. Some combination of these effects could selectively stabilize/destabilize some spin states. We found that the high spin state (Stotal = 6) of the oxyl–oxo species can be causative for cat...
収録刊行物
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- Journal of Chemical Theory and Computation
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Journal of Chemical Theory and Computation 15 (4), 2375-2391, 2019-03-11
American Chemical Society (ACS)
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詳細情報 詳細情報について
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- CRID
- 1360004233128977408
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- ISSN
- 15499626
- 15499618
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- 資料種別
- journal article
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- データソース種別
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- Crossref
- KAKEN
- OpenAIRE
