Concerted bond switching mechanism coupled with one-electron transfer for the oxygen-oxygen bond formation in the oxygen-evolving complex of photosystem II

Mitsuo Shoji, Hiroshi Isobe, Kizashi Yamaguchi

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2 Citations (Scopus)

Abstract

We here precisely analyzed the electronic structures during the oxygen-oxygen (O-O) bond formation of the oxygen-evolving complex (OEC) in photosystem II (PSII) based on the quantum mechanics/molecular mechanics (QM/MM) calculations. Changes in the spin density and the chemical indices derived from the natural orbitals suggested that the O(5)-O(6) bond formation proceeds with a concerted bond breaking of the Mn4-O(5) coupled with the through-bond one-electron transfer from the O(6) site to the Mn4 site (Mn4(IV) → Mn4(III)). This mechanism can be best described as a Concerted Bond Switching (CBS) mechanism, which is a non-radical reaction of the O(5)-O(6) bond formation.

Original languageEnglish
Pages (from-to)219-226
Number of pages8
JournalChemical Physics Letters
Volume714
DOIs
Publication statusPublished - Jan 16 2019

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Photosystem II Protein Complex
electron transfer
Oxygen
Electrons
oxygen
Molecular mechanics
Quantum theory
Electronic structure
quantum mechanics
electronic structure
orbitals

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

Cite this

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title = "Concerted bond switching mechanism coupled with one-electron transfer for the oxygen-oxygen bond formation in the oxygen-evolving complex of photosystem II",
abstract = "We here precisely analyzed the electronic structures during the oxygen-oxygen (O-O) bond formation of the oxygen-evolving complex (OEC) in photosystem II (PSII) based on the quantum mechanics/molecular mechanics (QM/MM) calculations. Changes in the spin density and the chemical indices derived from the natural orbitals suggested that the O(5)-O(6) bond formation proceeds with a concerted bond breaking of the Mn4-O(5) coupled with the through-bond one-electron transfer from the O(6) site to the Mn4 site (Mn4(IV) → Mn4(III)). This mechanism can be best described as a Concerted Bond Switching (CBS) mechanism, which is a non-radical reaction of the O(5)-O(6) bond formation.",
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T1 - Concerted bond switching mechanism coupled with one-electron transfer for the oxygen-oxygen bond formation in the oxygen-evolving complex of photosystem II

AU - Shoji, Mitsuo

AU - Isobe, Hiroshi

AU - Yamaguchi, Kizashi

PY - 2019/1/16

Y1 - 2019/1/16

N2 - We here precisely analyzed the electronic structures during the oxygen-oxygen (O-O) bond formation of the oxygen-evolving complex (OEC) in photosystem II (PSII) based on the quantum mechanics/molecular mechanics (QM/MM) calculations. Changes in the spin density and the chemical indices derived from the natural orbitals suggested that the O(5)-O(6) bond formation proceeds with a concerted bond breaking of the Mn4-O(5) coupled with the through-bond one-electron transfer from the O(6) site to the Mn4 site (Mn4(IV) → Mn4(III)). This mechanism can be best described as a Concerted Bond Switching (CBS) mechanism, which is a non-radical reaction of the O(5)-O(6) bond formation.

AB - We here precisely analyzed the electronic structures during the oxygen-oxygen (O-O) bond formation of the oxygen-evolving complex (OEC) in photosystem II (PSII) based on the quantum mechanics/molecular mechanics (QM/MM) calculations. Changes in the spin density and the chemical indices derived from the natural orbitals suggested that the O(5)-O(6) bond formation proceeds with a concerted bond breaking of the Mn4-O(5) coupled with the through-bond one-electron transfer from the O(6) site to the Mn4 site (Mn4(IV) → Mn4(III)). This mechanism can be best described as a Concerted Bond Switching (CBS) mechanism, which is a non-radical reaction of the O(5)-O(6) bond formation.

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