4.1 Article

RIXS at the cerium L3-edge of Ce(III) and Ce(IV) systems: some observations

Journal

CANADIAN JOURNAL OF CHEMISTRY
Volume 93, Issue 2, Pages 218-226

Publisher

CANADIAN SCIENCE PUBLISHING, NRC RESEARCH PRESS
DOI: 10.1139/cjc-2014-0261

Keywords

resonant inelastic X-ray scattering (RIXS); X-ray emission (XES); cerium L-3-edge; XANES; constant initial state (CIS); constant final state (CFS)

Funding

  1. NSERC
  2. CFI
  3. CRC
  4. OIT
  5. US Department of Energy, Basic Energy Sciences
  6. Canadian Light Source
  7. University of Washington
  8. Advanced Photon Source
  9. US Department of Energy [DE-AC02-06CH11357]

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We report recent observations of resonant inelastic X-ray scattering (RIXS) at the cerium L-3-edge of CePO4, CeO2, and Ce3+ ion in aqueous solution. The intensity of the emission spectrum, including the dispersive Raman below the edge and the emerging nondispersive fluorescence above the edge, was recorded with a solid-state detector with low-energy resolution and a WDX detector with modestly high-energy resolution. The yield of the emission was used to monitor the cerium L-3-edge X-ray absorption near edge structures (XANES) in a constant initial state (CIS) mode as the photon energy sweeps across the cerium L-3-edge. The CIS XANES is compared with the XANES recorded using the nondispersive fluorescence yield, L-alpha, in a constant final state (CFI) mode. It is found that the Raman yield dominates the total emission in the pre-edge region and diminishes rapidly at threshold. The RIXS of Ce3+ (i)n aqueous solution exhibits similar behavior as CePO4. The post-whiteline RIXS intensity of CePO4 exhibits a correlation with excitation energy. CeO2 also exhibits a less intense whiteline in CIS XANES compared with the XANES detected with normal fluorescence. The implications of these observations with improved instrumental resolution are noted.

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