Theory of chemical bonds in metalloenzymes XXIII fundamental principles for the photo-induced water oxidation in oxygen evolving complex of photosystem II

K. Yamaguchi, S. Yamanaka, H. Isobe, M. Shoji, K. Miyagawa, T. Kawakami

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Molecular quantum mechanics (MQM) investigations have been performed for elucidation of fundamental principles of the photo-induced water oxidation in oxygen evolving complex (OEC) of photosystem II (PSII). To this end, as a first theoretical step, broken symmetry (BS) quantum mechanics (QM) and QM(BS)/molecular mechanics (MM) calculations have been conducted for elucidation of geometrical, electronic and spin structures of the CaMn4Ox (X = 5, 6) cluster in the five steps Si (i = 0∼4) of the Kok cycle for water oxidation. The QM and QM/MM calculations have provided full optimised geometries of short-lived key intermediates and transition state structure for the O-O bond formation in the native solar-energy conversion. The interplay between theory and experiment have clearly indicated that the CaMn4O5 cluster in OEC of PSII exhibits typical physicochemical properties of strong correlation electron system (SCES) confined with effective protein field. Our QM and QM/MM computational results for key intermediates and transition structure for the O-O bond formation in the Kok cycle are now plentiful for derivation of fundamental principles (FP) for understanding of photo-induced water oxidation in OEC of PSII. We summarize twenty nine fundamental principles (FPs) in systematic manner by QM and QM/MM calculations for understanding of water oxidation in Oxygen Evolving Complex(OEC) of Photosystem II(PSII). One of our final aims is theoretical design of the next-generation artificial photosystem materials composed of abundant metal ions.

Original languageEnglish
Article numbere1725168
JournalMolecular Physics
Publication statusAccepted/In press - Jan 1 2020



  • CaMnO cluster
  • OECof PSII
  • Water oxidation
  • reaction mechanism

ASJC Scopus subject areas

  • Biophysics
  • Molecular Biology
  • Condensed Matter Physics
  • Physical and Theoretical Chemistry

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