Relative stability between the manganese hydroxide- and oxo-models for water oxidation by CCSD, DMRG CASCI, CASSCF, CASPT2 and CASDFT methods; Importance of static and dynamical electron correlation effects for OEC of PSII

T. Kawakami, K. Miyagawa, Hiroshi Isobe, M. Shoji, S. Yamanaka, M. Katouda, T. Nakajima, K. Nakatani, M. Okumura, K. Yamaguchi

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Relative stability between manganese hydroxide (H2O)2(OH)4Mn(IV)–OH (1) and manganese oxo (H2O)3(OH)3Mn(IV)[dbnd]O (2) species were investigated by coupled cluster (CC) SD and SD(T), DMRG CASCI, CASSCF, CASPT2 and CASDFT methods. The DMRG CASCI and DMRG CASSCF based on thirteen active orbitals and thirteen active electrons {13, 13} CAS space indicted the greater stability of 2 than 1. On the other hand, the relative stability between 1 and 2 was reversed by UCC SD, DLPNO-UCC SD, CASPT2 and CAS-DFT, indicating an important role of dynamical electron correlation corrections. Implications of present results are discussed to elucidate scope and applicability of hybrid DFT (HDFT) methods for 1 and 2.

Original languageEnglish
Pages (from-to)85-91
Number of pages7
JournalChemical Physics Letters
Publication statusPublished - Aug 1 2018



  • CaMnO cluster
  • CAS-DFT method
  • DMRG method
  • LPNO-CC method
  • OEC of PSII
  • Reaction mechanism
  • Water oxidation

ASJC Scopus subject areas

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

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