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Title: Vibrational properties of uranium fluorides

Journal Article · · Physica. B, Condensed Matter
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Multiphase mixtures of the uranium fluoride compounds UFx with x = 3, 4, 4.5, 5, whose local U–F bonding geometry is conserved, may result from UF6 reduction. One method for identifying multiphase mixtures is optical vibrational spectroscopy, but experimental Raman and IR spectra for UFx compounds are difficult to obtain. To supplement those experimental measurements, we use density functional perturbation theory (DFPT) with the on-site Coulomb correction (Hubbard + U) to calculate the phonon normal modes, their IR intensity, and their Raman activity for UF3, UF4, U2F9, and UF5. In addition, we use neutron spectroscopy to measure the phonon density of states of the most stable UF4. Our measurements on the Wide-Angular Range Chopper Spectrometer at the Spallation Neutron Source indicate that UF4 has a broad phonon spectrum centered at about 30 meV, but modeling of this spectrum indicates significant multiphonon scattering is present. DFPT calculations for U2F9, which shares structural features with UF4 and UF5, suggest a dynamic instability and we speculate that previous crystallographic measurements of this compound were possible only in multiphase mixtures. Analysis of the detailed atomic motions of phonons in UF5 indicate that a series of high energy modes (between 69 and 75 meV) are described by motion of single-coordinated F atoms (bonded to only one U atom). These single-coordinated F atoms are unique to the UF5 structure and those modes could be used to distinguish UF5 in a multiphase mixture using optical spectroscopy.

Research Organization:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
Sponsoring Organization:
USDOE
Grant/Contract Number:
AC05-00OR22725
OSTI ID:
1564411
Alternate ID(s):
OSTI ID: 1542246
Journal Information:
Physica. B, Condensed Matter, Journal Name: Physica. B, Condensed Matter Vol. 570 Journal Issue: C; ISSN 0921-4526
Publisher:
ElsevierCopyright Statement
Country of Publication:
Netherlands
Language:
English
Citation Metrics:
Cited by: 4 works
Citation information provided by
Web of Science

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Figures / Tables (14)

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Related Subjects

75 CONDENSED MATTER PHYSICS
SUPERCONDUCTIVITY AND SUPERFLUIDITY
Uranium
Phonons
Density functional theory
Inelastic neutron scattering
Lattice dynamics