A Theoretical Study of the Recently Suggested Mn(VII) Mechanism for O–O Bond Formation in Photosystem II

[Image: see text] The mechanism for water oxidation in photosystem II has been a major topic for several decades. The active catalyst has four manganese atoms connected by bridging oxo bonds, in a complex termed the oxygen-evolving complex (OEC), which also includes a calcium atom. The O–O bond of oxygen is formed after absorption of four photons in a state of the OEC termed S(4). There has been essential consensus that in the S(4) state, all manganese atoms are in the Mn(IV) oxidation state. However, recently there has been a suggestion that one of the atoms is in the Mn(VII) state. In the present computational study, the feasibility of that proposal has been investigated. It is here shown that the mechanism involving Mn(VII) has a much higher barrier for forming O(2) than the previous proposal with four Mn(IV) atoms.