Details

Autor(en) / Beteiligte

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

Titel

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

Ist Teil von

• Chemical physics letters, 2018-08, Vol.705, p.85-91

Ort / Verlag

Elsevier B.V

Erscheinungsjahr

2018

Link zum Volltext

Quelle

Alma/SFX Local Collection

Beschreibungen/Notizen

• [Display omitted] •The OO bond formation in high-valent manganese oxo species (MnO) has been considered to be the most important process for water oxidation in OEC of PSII.•In order to study proton-shift reaction in S3 state in Kok cycle, relative stability between manganese hydroxide (H2O)2(OH)4Mn(IV)OH (1) and manganese oxo (H2O)3(OH)3Mn(IV)O (2) molecules were investigated by coupled cluster (CC) SD(T), DMRG CASCI, CASSCF, CASPT2 and CAS-DFT methods. Relative stability between manganese hydroxide (H2O)2(OH)4Mn(IV)OH (1) and manganese oxo (H2O)3(OH)3Mn(IV)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.