Nonadiabatic one-electron transfer mechanism for the O-O bond formation in the oxygen-evolving complex of photosystem II

被引：28

作者：

Shoji, Mitsuo ^{[1
]}

Isobe, Hiroshi ^{[2
]}

Shigeta, Yasuteru ^{[1
]}

Nakajima, Takahito ^{[3
]}

Yamaguchi, Kizashi ^{[4
,5
]}

机构：

[1] Univ Tsukuba, Ctr Computat Sci, Tennodai 1-1-1, Tsukuba, Ibaraki 3058577, Japan

[2] Okayama Univ, Grad Sch Nat Sci & Technol, Fac Sci, Okayama 7008530, Japan

[3] Riken Adv Inst Computat Sci, Kobe, Hyogo 6500047, Japan

[4] Osaka Univ, Inst NanoSci Design, Toyonaka, Osaka 5608531, Japan

[5] Handairigaku Technores NPO, Toyonaka, Osaka 5600043, Japan

来源：

CHEMICAL PHYSICS LETTERS | 2018年 / 698卷

关键词：

CATALYTIC WATER OXIDATION; SCALE QM/MM CALCULATIONS; DIOXYGEN FORMATION; CRYSTAL-STRUCTURE; SUBSTRATE-WATER; S-3; TRANSITION; CHEMICAL-BONDS; MANGANESE-OXO; EVOLUTION; BINDING;

D O I：

10.1016/j.cplett.2018.02.056

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

The reaction mechanism of the O-2 formation in the S-4 state of the oxygen-evolving complex of photosystem II was clarified at the quantum mechanics/molecular mechanics (QM/MM) level. After the Yz (Y161) oxidation and the following proton transfer in the S-3 state, five reaction steps are required to produce the molecular dioxygen. The highest barrier step is the first proton transfer reaction (0 -> 1). The following reactions involving electron transfers were precisely analyzed in terms of their energies, structures and spin densities. We found that the one-electron transfer from the Mn4Ca cluster to Y161 triggers the O-O sigma bond formation. (C) 2018 Elsevier B.V. All rights reserved.

引用

页码：138 / 146

页数：9

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