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Towards a comprehensive X-ray approach for studying the photosynthetic manganese complex–XANES, Kα/Kβ/Kβ-satellite emission lines, RIXS, and comparative computational approaches for selected model complexes

I Zaharieva et al 2009 J. Phys.: Conf. Ser. 190 012142 (6pp)   doi: 10.1088/1742-6596/190/1/012142  Help

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I Zaharieva1, P Chernev1, M Risch1, L Gerencser1, G Berggren2, D Shevchenko2, M Anderlund2, T C Weng3, M Haumann1,4 and H Dau1,4
1 Free University Berlin, FB Physik, Arnimallee 14, D-14195 Berlin, Germany
2 Dept. of Photochemistry and Molecular Science, Uppsala University, Box 523, S-751 20 Uppsala, Sweden
3 European Synchrotron Radiation Facility, BP 220, F-38043 Grenoble Cedex, France
4 Corresponding authors
E-mail: holger.dau@fu-berlin.de and michael.haumann@fu-berlin.de

Abstract. Advanced X-ray spectroscopy experiments can contribute to elucidation of the mechanism of water oxidation in biological (tetra-manganese complex of Photosystem II) and artificial systems. Although the electronic structure of the catalytic metal site is of high interest, it is experimentally not easily accessible. Therefore, we and other researchers are working towards a comprehensive approach involving a combination of methods, namely (1) quantitative analysis of X-ray absorption near-edge structure (XANES) spectra collected at the K-edge and, in the long run, at the L-edge of manganese; (2) high-resolution X-ray emission spectroscopy (XES) of Kα and Kβ lines, (3) two-dimensional resonant inelastic X-ray scattering (RIXS) spectra. Collection of these spectroscopic data sets requires state-of-the-art synchrotron radiation facilities as well as experimental strategies to minimize the radiation-induced modifications of the samples. Data analysis requires the use and development of appropriate theoretical tools. Here, we present exemplary data collected for three multi-nuclear synthetic Mn complexes with the Mn ions in the oxidation states II, III, and IV, and for MnVII of the permanganate ion. Emission spectra are calculated for the MnVII ion using both multiple-scattering (MS) approach and time-dependent density functional theory (TDDFT).

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