Possible mechanisms for the O-O bond formation in oxygen evolution reaction at the CaMn4O5(H2O)4 cluster of PSII refined to 1.9 X-ray resolution

S. Yamanaka, H. Isobe, K. Kanda, T. Saito, Yasufumi Umena, K. Kawakami, J. R. Shen, N. Kamiya, M. Okumura, H. Nakamura, K. Yamaguchi

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Abstract

Very recently Umena et al. have determined the X-ray diffraction (XRD) structure of the CaMn4O5 cluster (1) in the oxygen-evolving complex (OEC) of photosystem II (PSII) refined to 1.9 resolution. UB3LYP calculations of 1 using this XRD structure were performed to elucidate possible mechanisms for the oxygen-oxygen (O-O) bond formation in oxygen evolution reaction of PSII. The solutions obtained were used for natural orbital (NO) analysis to obtain LUMOs of labile chemical bonds, which clearly indicated the possibilities of nucleophilic attack of hydroxide (or water molecule) to the electrophilic O(56) and/or O(57) sites of 1.

Original languageEnglish
Pages (from-to)138-145
Number of pages8
JournalChemical Physics Letters
Volume511
Issue number1-3
DOIs
Publication statusPublished - Jul 26 2011

ASJC Scopus subject areas

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

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