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Marilyn R. Gunner

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The Oxygen Evolving Complex (OEC) of Photosystem II (PSII) is a unique Mn4O5Ca2+ cluster that catalyzes the photoactivated water splitting reaction. The OEC is a model system for bio-inspired artificial systems to use solar energy to pull electrons from water to produce fuel. The OEC goes through a cycle of 5 S states storing 4 holes, via electron transfer to P680+, the primary electron donor in PSII to generate a high valence S4 state that oxidizes water. The key questions are what controls the order of oxidation and deprotonation of the OEC complex and how does the PSII protein modulate the cluster behavior. Here, we present a classical electrostatics Monte Carlo (MC) technique, with input from density functional theory (DFT) and molecular dynamics (MD) to study the thermodynamics of the S0 to S3 states in a cluster embedded in the whole PSII. The model is tested against model complexes and yields a very good agreement with the experiment. In the simulation, the electrochemical potential (Eh) is varied to oxidize the OEC. The MC sampling allows the �µ-oxo-bridges, terminal waters and amino acid residues to change their protonation states and/or their rotamer position to respond to the Mn oxidation. In addition, chloride is allowed to move during the cycle. The order of Mn oxidation found here is Mn2, Mn3, Mn4 and finally Mn1 as the system goes from the S0 to S3 states. In the S-1 state O1 and O4 are protonated as are the terminal waters on Mn4 and the Ca2+. O4 and O1 are deprotonated when S0 and S1 are formed respectively. The formation of S2 includes proton transfer from W2 to the nearby D61, reducing the release of protons to the media, consistent with experimental measurements. Protons are also lost from H337 and E329. The proton-release pattern is compared fixing the protonation states for H337, D61, terminal waters and with chloride-depleted PSII. The calculated midpoint potential of each Mn and their dependence on pH is discussed.

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