Effect of Charge Distribution over a Chlorophyll Dimer on the Redox Potential of P680 in Photosystem II As Studied by Density Functional Theory Calculations
journal contributionposted on 17.06.2008 by Ryouta Takahashi, Koji Hasegawa, Takumi Noguchi
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The effect of charge distribution over a chlorophyll dimer on the redox potential of P680 in photosystem II was studied by density functional theory calculations using the P680 coordinates in the X-ray structure. From the calculated ionization potentials of the dimer and the monomeric constituents, the decrease in the redox potential by charge delocalization over the dimer was estimated to be ∼140 mV. Such charge delocalization was previously observed in the isolated D1−D2−Cyt b559 complexes, whereas the charge was primarily localized on PD1 in the core complexes. The calculated potential decrease of ∼140 mV can explain the inhibition of YZ oxidation in the former complexes and in turn implies that the charge localization on PD1 upon formation of the core complex increases the P680 potential to the level necessary for water oxidation.