Theoretical and computational investigations of geometrical, electronic and spin structures of the CaMn 4 O X (X = 5, 6) cluster in the Kok cycle S i (i = 0–3) of oxygen evolving complex of photosystem II

Kizashi Yamaguchi, Shusuke Yamanaka, Hiroshi Isobe, Mitsuo Shoji, Kouichi Miyagawa, Takahito Nakajima, Takashi Kawakami, Mitsutaka Okumura

Research output: Contribution to journalArticle

4 Citations (Scopus)

Abstract

The optimized geometries of the CaMn 4 O X (X = 5, 6) cluster in the oxygen evolving complex (OEC) of photosystem II (PSII) by large-scale quantum mechanics (QM) and molecular mechanics (MM) calculations are compared with recent serial femtosecond crystallography (SFX) results for the S i (i = 0–3) states. The valence states of four Mn ions by the QM/MM calculations are also examined in relation to the experimental results by the X-ray emission spectroscopy (XES) for the S i intermediates. Geometrical and valence structures of right-opened Mn-hydroxide, Mn-oxo and Mn-peroxide intermediates in the S 3 state are investigated in detail in relation to recent SFX and XES experiments for the S 3 state. Interplay between theory and experiment indicates that the Mn-oxo intermediate is a new possible candidate for the S 3 state. Implications of the computational results are discussed in relation to possible mechanisms of the oxygenoxygen bond formation for water oxidation in OEC of PSII.

Original languageEnglish
Pages (from-to)44-59
Number of pages16
JournalPhysiologia Plantarum
Volume166
Issue number1
DOIs
Publication statusPublished - May 2019

ASJC Scopus subject areas

  • Physiology
  • Genetics
  • Plant Science
  • Cell Biology

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