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.

doi:10.1021/acs.jpcc.5b10610

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

Journal Article · Tue Jan 19 00:00:00 EST 2016 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.5b10610· OSTI ID:1239425

Davis, Katherine M. ^[1]; Palenik, Mark C. ^[1]; Yan, Lifen ^[1]; Smith, Paul F. ^[2]; Seidler, Gerald T. ^[3]; Dismukes, G. Charles ^[2]; Pushkar, Yulia N. ^[1]

Purdue Univ., West Lafayette, IN (United States)
Rutgers Univ., Piscataway, NJ (United States)
Univ. of Washington, Seattle, WA (United States)

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 demonstrates 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.

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Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)

Grant/Contract Number:: DGE0833366; DGE0903675; FG02-09ER16106; AC02-06CH11357

OSTI ID:: 1239425

Journal Information:: Journal of Physical Chemistry. C, Vol. 120, Issue 6; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: ENGLISH

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Cited by: 24 works

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