A Theoretical Study of the Recently Suggested MnVII Mechanism for O-O Bond Formation in Photosystem II

被引：7

作者：

Li, Xi-Chen ^{[1
]}

Li, Jing ^{[1
]}

Siegbahn, Per E. M. ^{[2
]}

机构：

[1] Beijing Normal Univ, Coll Chem, Beijing 100875, Peoples R China

[2] Stockholm Univ, Dept Organ Chem, Arrhenius Lab, SE-10691 Stockholm, Sweden

来源：

JOURNAL OF PHYSICAL CHEMISTRY A | 2020年 / 124卷 / 39期

基金：

瑞典研究理事会; 中国国家自然科学基金;

关键词：

OXYGEN-EVOLVING COMPLEX; WATER OXIDATION; PROTON RELEASE; S-2; STATE; RESOLUTION; CHEMISTRY; KINETICS; SITE;

D O I：

10.1021/acs.jpca.0c05135

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 mechanism for water oxidation in photosystem II has been a major topic for several decades. The active catalyst has four manganese atoms connected by bridging oxo bonds, in a complex termed the oxygen-evolving complex (OEC), which also includes a calcium atom. The O-O bond of oxygen is formed after absorption of four photons in a state of the OEC termed S-4. There has been essential consensus that in the S-4 state, all manganese atoms are in the Mn(IV) oxidation state. However, recently there has been a suggestion that one of the atoms is in the Mn(VII) state. In the present computational study, the feasibility of that proposal has been investigated. It is here shown that the mechanism involving Mn(VII) has a much higher barrier for forming O-2 than the previous proposal with four Mn(IV) atoms.

引用

页码：8011 / 8018

页数：8

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