Water oxidation mechanism in photosystem II, including oxidations, proton release pathways, O―O bond formation and O2 release

AbstractThe present status of DFT studies on water oxidation in photosystem II is described. It is argued that a full understanding of all steps is close. In each S-transition, the manganese that is oxidized and the proton released are strongly implicated, and structures of all intermediates have been determined. For the S2-state, recent important experimental findings support key elements of the structure and the mechanism. In this mechanism, the O―O bond is formed between an oxyl radical in the center of the cluster and an Mn-bridging μ-oxo ligand, which was suggested already in 2006. The DFT structure of the oxygen evolving complex, suggested in 2008, is very similar to the recent high-resolution X-ray structure. Some new aspects of the interaction between P680 and the OEC are suggested. This article is part of a Special Issue entitled: Metals in Bioenergetics and Biomimetics Systems