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Ruthenium 4d-to-2p X-ray Emission Spectroscopy: A Simultaneous Probe of the Metal and the Bound Ligands

MPS-Authors

Levin,  Natalia
Research Department DeBeer, Max Planck Institute for Chemical Energy Conversion, Max Planck Society;

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Peredkov,  Sergey
Research Department DeBeer, Max Planck Institute for Chemical Energy Conversion, Max Planck Society;

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Weyhermüller,  Thomas
Research Department DeBeer, Max Planck Institute for Chemical Energy Conversion, Max Planck Society;

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Rüdiger,  Olaf
Research Department DeBeer, Max Planck Institute for Chemical Energy Conversion, Max Planck Society;

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DeBeer,  Serena
Research Department DeBeer, Max Planck Institute for Chemical Energy Conversion, Max Planck Society;

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Citation

Levin, N., Peredkov, S., Weyhermüller, T., Rüdiger, O., Pereira, N. B., Grötzsch, D., et al. (2020). Ruthenium 4d-to-2p X-ray Emission Spectroscopy: A Simultaneous Probe of the Metal and the Bound Ligands. Inorganic Chemistry, 59(12), 8272-8283. doi:10.1021/acs.inorgchem.0c00663.


Cite as: http://hdl.handle.net/21.11116/0000-0007-B456-D
Abstract
Ruthenium 4d-to-2p X-ray emission spectroscopy (XES) was systematically explored for a series of Ru2+ and Ru3+ species. Complementary density functional theory calculations were utilized to allow for a detailed assignment of the experimental spectra. The studied complexes have a range of different coordination spheres, which allows the influence of the ligand donor/acceptor properties on the spectra to be assessed. Similarly, the contributions of the site symmetry and the oxidation state of the metal were analyzed. Because the 4d-to-2p emission lines are dipole-allowed, the spectral features are intense. Furthermore, in contrast with K- or L-edge X-ray absorption of 4d transition metals, which probe the unoccupied levels, the observed 4p-to-2p XES arises from electrons in filled-ligand- and filled-metal-based orbitals, thus providing simultaneous access to the ligand and metal contributions to bonding. As such, 4d-to-2p XES should be a promising tool for the study of a wide range of 4d transition-metal compounds.