Print Email Facebook Twitter Crystal-Field and Covalency Effects in Uranates Title Crystal-Field and Covalency Effects in Uranates: An X-ray Spectroscopic Study Author Butorin, Sergei M. (Uppsala University) Kvashnina, Kristina O. (Helmholtz Zentrum Dresden Rossendorf; European Synchrotron Radiation Facility (ESRF)) Smith, A.L. (TU Delft RST/Reactor Physics and Nuclear Materials) Popa, Karin (European Commission Joint Research Centre, Institute for Transuranium Elements Karlsruhe) Martin, Philippe M. (UMR 5257 CEA/CNRS/UM/ENSCM) Date 2016 Abstract The electronic structure of UV- and UVI-containing uranates NaUO3and Pb3UO6was studied by using an advanced technique, namely X-ray absorption spectroscopy (XAS) in high-energy-resolution fluorescence-detection (HERFD) mode. Due to a significant reduction in core–hole lifetime broadening, the crystal-field splittings of the 5f shell were probed directly in HERFD-XAS spectra collected at the U 3d edge, which is not possible by using conventional XAS. In addition, the charge-transfer satellites that result from U 5f–O 2p hybridization were clearly resolved. The crystal-field parameters, 5f occupancy, and degree of covalency of the chemical bonding in these uranates were estimated by using the Anderson impurity model by calculating the U 3d HERFD-XAS, conventional XAS, core-to-core (U 4f–3d transitions) resonant inelastic X-ray scattering (RIXS), and U 4f X-ray photoelectron spectra. The crystal field was found to be strong in these systems and the 5f occupancy was determined to be 1.32 and 0.84 electrons in the ground state for NaUO3and Pb3UO6, respectively, which indicates a significant covalent character for these compounds. Subject computational chemistrycrystal-field studieselectronic structureuraniumX-ray absorption spectroscopy To reference this document use: http://resolver.tudelft.nl/uuid:5b6f2d4b-63e0-4540-8a31-ee8674724728 DOI https://doi.org/10.1002/chem.201505091 Embargo date 2017-06-03 ISSN 0947-6539 Source Chemistry: A European Journal, 22 (28), 9693-9698 Bibliographical note Accepted Author Manuscript Part of collection Institutional Repository Document type journal article Rights © 2016 Sergei M. Butorin, Kristina O. Kvashnina, A.L. Smith, Karin Popa, Philippe M. Martin Files PDF Uranates_acs_rvd_nored_final.pdf 461.86 KB Close viewer /islandora/object/uuid:5b6f2d4b-63e0-4540-8a31-ee8674724728/datastream/OBJ/view