Polarized X-ray Absorption Spectroscopy of Single-crystal Mn(V)Complexes Relevant to the Oxygen-Evolving Complex of Photosystem II
High-valent Mn=O species have been suggested to have acatalytically important role in the water splitting reaction which occursin the Photosystem II membrane protein. In this study, five- andsix-coordinate mononuclear Mn(V) compounds were investigated by polarizedX-ray absorption spectroscopy in order to understand the electronicstructure and spectroscopic characteristics of high-valent Mn species.Single crystals of the Mn(V)-nitrido and Mn(V)-oxo compounds were alignedalong selected molecular vectors with respect to the X-ray polarizationvector using X-ray diffraction. The local electronic structure of themetal site was then studied by measuring the polarization dependence ofX-ray Absorption Near Edge Spectroscopy (XANES) pre-edge spectra (1s to3d transition) and comparing with the results of density functionaltheory (DFT) calculations. The Mn(V)-nitrido compound, in which themanganese is coordinated in a tetragonally distorted octahedralenvironment, showed a single dominant pre-edge peak along the Mn?N axisthat can be assigned to a strong 3dz2 - 4pz mixing mechanism. In thesquare pyramidal Mn(V)-oxo system, on the other hand, an additional peakwas observed at 1eV below the main pre-edge peak. This component, whichdoes not show noticeable dichroism, was interpreted as a 1s to 3dxz, yztransition with 4px,y mixing, due to the displacement of the Mn atom outof the equatorial plane. The XANES results have been correlated to DFTcalculations, and the spectra have been simulated using a TD (timedependent)-DFT approach. The relevance of these results to understandingthe mechanism of the photosynthetic water oxidation isdiscussed.
- Research Organization:
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
- Sponsoring Organization:
- USDOE Director, Office of Science; National Institutes ofHealth
- DOE Contract Number:
- DE-AC02-05CH11231; NIHGM 55302
- OSTI ID:
- 929666
- Report Number(s):
- LBNL-62495; JACSAT; R&D Project: 864N1F; BnR: 400412000; TRN: US200812%%739
- Journal Information:
- Journal of the American Chemical Society, Vol. 129, Issue 43; Related Information: Journal Publication Date: 2007; ISSN 0002-7863
- Country of Publication:
- United States
- Language:
- English
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