X-ray Emission Spectroscopy of Mn Coordination Complexes Toward Interpreting the Electronic Structure of the Oxygen-Evolving Complex of Photosystem II

Katherine M. Davis, Mark C. Palenik, Lifen Yan, Paul F. Smith, Gerald T. Seidler, G. Charles Dismukes, Yulia N. Pushkar

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20 Citations (Scopus)


X-ray emission (XES) spectroscopy is an attractive technique for analysis of the electronic structure of molecules, materials, and metalloproteins. However, a better understanding of XES results is required. Using a combination of experiment and ground-state density functional theory analysis, we rationalize differences in the X-ray emission spectra of multinuclear Mn complexes. Model compounds, including dinuclear [Mn2O2L′4](ClO4)3 (L′= 2,2′-bipyridyl, [1]) and two examples from the Mn4O4L6 "cubane " family of model compounds (L = (p-R-C6H4)PO2¯, R = OCH3 [2], CH3 [3]), were compared with the Oxygen Evolving Complex of Photosystem II. Our analysis shows that changes in the structure of the Mn complexes, resulting in changes to the spin polarization, can introduce significant spectral shifts in compounds of the same formal redox state. The implications of changes in spin polarization for understanding photosynthetic water-splitting catalysis is discussed.

Original languageEnglish
Pages (from-to)3326-3333
Number of pages8
JournalJournal of Physical Chemistry C
Issue number6
Publication statusPublished - Feb 18 2016


ASJC Scopus subject areas

  • Electronic, Optical and Magnetic Materials
  • Energy(all)
  • Physical and Theoretical Chemistry
  • Surfaces, Coatings and Films

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