Crystal-Field and Covalency Effects in Uranates: An X-ray Spectroscopic Study

Sergei M. Butorin, Kristina O. Kvashnina, Anna L. Smith, Karin Popa, Philippe M. Martin

Research output: Contribution to journalArticleScientificpeer-review

15 Citations (Scopus)
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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.

Original languageEnglish
Pages (from-to)9693-9698
Number of pages6
JournalChemistry: A European Journal
Volume22
Issue number28
DOIs
Publication statusPublished - 2016

Bibliographical note

Accepted Author Manuscript

Keywords

  • computational chemistry
  • crystal-field studies
  • electronic structure
  • uranium
  • X-ray absorption spectroscopy

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