Theoretical investigations of structure and mechanism of the oxygen-evolving complex in PSII

被引：81

作者：

Lundberg, M ^{[1
]}

Siegbahn, PEM ^{[1
]}

机构：

[1] Stockholm Univ, Dept Phys, AlbaNova Univ Ctr, Stockholm Ctr Phys Astron & Biotechnol, SE-10691 Stockholm, Sweden

来源：

PHYSICAL CHEMISTRY CHEMICAL PHYSICS | 2004年 / 6卷 / 20期

关键词：

D O I：

10.1039/b406552b

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：

Hybrid density functional theory has been used to study a proposed Mn3Ca-Mn cubane-like structure for the oxygen-evolving complex in photosystem II. A refined analysis of the structure is made regarding the position of the heavy atoms, the oxidation states of the manganese centers and the protonation states of the ligands. After finding the most stable S-2 structure, S-0 --> S-1 and S-1 --> S-2 transitions are proposed. Further, proposals for the higher S state transitions, S-2 --> S-3 and S-3 --> S-4 have been investigated, using the O-H bond dissociation energy as a probe. With an intact cubane-like structure, oxidation to a high valent Mn-oxo species has so far not been found to be energetically feasible. Instead, tentative proposals of the S-2 --> S-3 transition involving structural rearrangements are made.

引用

页码：4772 / 4780

页数：9

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