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Electronic Structure and Oxidation State Changes in the Mn (4) Ca Cluster of Photosystem II [electronic resource].

Published
Washington, D.C. : United States. Dept. of Energy. Office of Science, 2012.
Oak Ridge, Tenn. : Distributed by the Office of Scientific and Technical Information, U.S. Dept. of Energy.
Additional Creators
SLAC National Accelerator Laboratory, United States. Department of Energy. Office of Science, and United States. Department of Energy. Office of Scientific and Technical Information
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Summary
Oxygen-evolving complex (Mn₄Ca cluster) of Photosystem II cycles through five intermediate states (S{sub i}-states, i = 0-4) before a molecule of dioxygen is released. During the S-state transitions, electrons are extracted from the OEC, either from Mn or alternatively from a Mn ligand. The oxidation state of Mn is widely accepted as Mn₄(III₂,IV₂) and Mn₄(III,IV₃) for S₁ and S₂ states, while it is still controversial for the S₀ and S₃ states. We used resonant inelastic X-ray scattering (RIXS) to study the electronic structure of Mn₄Ca complex in the OEC. The RIXS data yield two-dimensional plots that provide a significant advantage by obtaining both K-edge pre-edge and L-edge-like spectra (metal spin state) simultaneously. We have collected data from PSII samples in the each of the S-states and compared them with data from various inorganic Mn complexes. The spectral changes in the Mn 1s2p{sub 3/2} RIXS spectra between the S-states were compared to those of the oxides of Mn and coordination complexes. The results indicate strong covalency for the electronic configuration in the OEC, and we conclude that the electron is transferred from a strongly delocalized orbital, compared to those in Mn oxides or coordination complexes. The magnitude for the S₀ to S₁, and S₁ to S₂ transitions is twice as large as that during the S₂ to S₃ transition, indicating that the electron for this transition is extracted from a highly delocalized orbital with little change in charge density at the Mn atoms.
Report Numbers
E 1.99:slac-pub-15218
slac-pub-15218
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Note
Published through SciTech Connect.
08/17/2012.
"slac-pub-15218"
Springer Netherlands FT
Bergmann, U.; Yachandra, V.K.; Glatzel, P.; Yano, J.; Pushkar, Y.; Messinger, J.
Funding Information
AC02-76SF00515
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