Elucidation of a multiple S3 intermediates model for water oxidation in the oxygen evolving complex of photosystem II. Calcium-assisted concerted OO bond formation

[Display omitted] •Several S3 intermediates for CaMn4O6 cluster of OEC of PSII were investigated by hybrid DFT and DLPNO-CC calculations.•The experimental geometries in the S3 state were compared and weighted estimated from the optimized geometries.•Mn-hydroxide and Mn-Oxyl intermediates are the mai...

Full description

Saved in:
Bibliographic Details
Published in:Chemical physics letters 2022-11, Vol.806, Article 140042
Main Authors: Yamaguchi, Kizashi, Miyagawa, Koichi, Shoji, Mitsuo, Isobe, Hiroshi, Kawakami, Takashi
Format: Article
Language:English
Subjects:
Mn-Oxyl intermediate
Multiple intermediate
Oxygen evolving complex
Photosystem II
S3 state
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
Description
Summary:[Display omitted] •Several S3 intermediates for CaMn4O6 cluster of OEC of PSII were investigated by hybrid DFT and DLPNO-CC calculations.•The experimental geometries in the S3 state were compared and weighted estimated from the optimized geometries.•Mn-hydroxide and Mn-Oxyl intermediates are the main intermediates in the multiple intermediates model. A multiple S3 intermediates model for water oxidation in the oxygen evolving complex (OEC) of photosystem II (PSII) is examined on the basis of key intermediates elucidated by UB3LYP/def2-TZVP and DLPNO-CCSD(T0) computations. The kinetic experimental results by this model are consistent with the main contribution of the Mn-Hydroxide configuration and partial contribution of Mn-Oxyl in the S3 state, for which the oxyl-radical character is largely reduced by the coordination of the Ca ion in OEC of PSII.
ISSN:0009-2614
1873-4448
DOI:10.1016/j.cplett.2022.140042