Theoretical elucidation of the structure, bonding, and reactivity of the CaMn₄O_x clusters in the whole Kok cycle for water oxidation embedded in the oxygen evolving center of photosystem II. New molecular and quantum insights into the mechanism of the O-O bond formation.

ABSTRACT: This paper reviews our historical developments of broken-symmetry (BS) and beyond BS methods that are applicable for theoretical investigations of metalloenzymes such as OEC in PSII. The BS hybrid DFT (HDFT) calculations starting from high-resolution (HR) XRD structure in the most stable S₁ state have been performed to elucidate structure and bonding of whole possible intermediates of the CaMn₄O_x cluster (1) in the S_i (i = 0 ~ 4) states of the Kok cycle. The large-scale HDFT/MM computations starting from HR XRD have been performed to elucidate biomolecular system structures which are crucial for examination of possible water inlet and proton release pathways for water oxidation in OEC of PSII. DLPNO CCSD(T₀) computations have been perf

SUBMITTER: Yamaguchi K 

PROVIDER: S-EPMC11614991 | biostudies-literature | 2024 Dec

REPOSITORIES: biostudies-literature