A Theoretical Study of the Recently Suggested Mn(VII) Mechanism for O–O Bond Formation in Photosystem II

[Image: see text] 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 o...

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Autores principales: Li, Xi-Chen, Li, Jing, Siegbahn, Per E. M.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2020
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7586388/
https://www.ncbi.nlm.nih.gov/pubmed/32877196
http://dx.doi.org/10.1021/acs.jpca.0c05135
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author Li, Xi-Chen
Li, Jing
Siegbahn, Per E. M.
author_facet Li, Xi-Chen
Li, Jing
Siegbahn, Per E. M.
author_sort Li, Xi-Chen
collection PubMed
description [Image: see text] 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.
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spelling pubmed-75863882020-10-27 A Theoretical Study of the Recently Suggested Mn(VII) Mechanism for O–O Bond Formation in Photosystem II Li, Xi-Chen Li, Jing Siegbahn, Per E. M. J Phys Chem A [Image: see text] 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. American Chemical Society 2020-09-02 2020-10-01 /pmc/articles/PMC7586388/ /pubmed/32877196 http://dx.doi.org/10.1021/acs.jpca.0c05135 Text en This is an open access article published under a Creative Commons Attribution (CC-BY) License (http://pubs.acs.org/page/policy/authorchoice_ccby_termsofuse.html) , which permits unrestricted use, distribution and reproduction in any medium, provided the author and source are cited.
spellingShingle Li, Xi-Chen
Li, Jing
Siegbahn, Per E. M.
A Theoretical Study of the Recently Suggested Mn(VII) Mechanism for O–O Bond Formation in Photosystem II
title A Theoretical Study of the Recently Suggested Mn(VII) Mechanism for O–O Bond Formation in Photosystem II
title_full A Theoretical Study of the Recently Suggested Mn(VII) Mechanism for O–O Bond Formation in Photosystem II
title_fullStr A Theoretical Study of the Recently Suggested Mn(VII) Mechanism for O–O Bond Formation in Photosystem II
title_full_unstemmed A Theoretical Study of the Recently Suggested Mn(VII) Mechanism for O–O Bond Formation in Photosystem II
title_short A Theoretical Study of the Recently Suggested Mn(VII) Mechanism for O–O Bond Formation in Photosystem II
title_sort theoretical study of the recently suggested mn(vii) mechanism for o–o bond formation in photosystem ii
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7586388/
https://www.ncbi.nlm.nih.gov/pubmed/32877196
http://dx.doi.org/10.1021/acs.jpca.0c05135
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