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

Research output: Contribution to journalArticle

18 Citations (Scopus)

Abstract

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
Volume120
Issue number6
DOIs
Publication statusPublished - Feb 18 2016

Fingerprint

Spin polarization
Photosystem II Protein Complex
Coordination Complexes
Electronic structure
Metalloproteins
Oxygen
electronic structure
X rays
2,2'-Dipyridyl
oxygen
Ground state
spectroscopy
Catalysis
Density functional theory
cubane
water splitting
x rays
polarization
Molecules
catalysis

ASJC Scopus subject areas

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

Cite this

X-ray Emission Spectroscopy of Mn Coordination Complexes Toward Interpreting the Electronic Structure of the Oxygen-Evolving Complex of Photosystem II. / Davis, Katherine M.; Palenik, Mark C.; Yan, Lifen; Smith, Paul F.; Seidler, Gerald T.; Dismukes, G Charles; Pushkar, Yulia N.

In: Journal of Physical Chemistry C, Vol. 120, No. 6, 18.02.2016, p. 3326-3333.

Research output: Contribution to journalArticle

Davis, Katherine M. ; Palenik, Mark C. ; Yan, Lifen ; Smith, Paul F. ; Seidler, Gerald T. ; Dismukes, G Charles ; Pushkar, Yulia N. / X-ray Emission Spectroscopy of Mn Coordination Complexes Toward Interpreting the Electronic Structure of the Oxygen-Evolving Complex of Photosystem II. In: Journal of Physical Chemistry C. 2016 ; Vol. 120, No. 6. pp. 3326-3333.
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