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 language | English |
|---|---|
| Pages (from-to) | 3326-3333 |
| Number of pages | 8 |
| Journal | Journal of Physical Chemistry C |
| Volume | 120 |
| Issue number | 6 |
| DOIs | |
| Publication status | Published - Feb 18 2016 |
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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 journal › Article
}
TY - JOUR
T1 - X-ray Emission Spectroscopy of Mn Coordination Complexes Toward Interpreting the Electronic Structure of the Oxygen-Evolving Complex of Photosystem II
AU - Davis, Katherine M.
AU - Palenik, Mark C.
AU - Yan, Lifen
AU - Smith, Paul F.
AU - Seidler, Gerald T.
AU - Dismukes, G Charles
AU - Pushkar, Yulia N.
PY - 2016/2/18
Y1 - 2016/2/18
N2 - 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.
AB - 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.
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U2 - 10.1021/acs.jpcc.5b10610
DO - 10.1021/acs.jpcc.5b10610
M3 - Article
VL - 120
SP - 3326
EP - 3333
JO - Journal of Physical Chemistry C
JF - Journal of Physical Chemistry C
SN - 1932-7447
IS - 6
ER -