Vibrational properties of uranium fluorides

Miskowiec, Andrew J.; Shields, Ashley E.; Niedziela, Jennifer L.; Cheng, Yongqiang; Taylor, Paul Allen; DelCul, Guillermo; Hunt, Rodney Dale; Spencer, Barry B.; Langford, Jr., John; Abernathy, Douglas L.

doi:10.1016/j.physb.2019.06.049

Title: Vibrational properties of uranium fluorides

Journal Article · 23 June 2019 · Physica. B, Condensed Matter

DOI: https://doi.org/10.1016/j.physb.2019.06.049 · OSTI ID:1542246

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Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

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.

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Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 1542246

Alternate ID(s):: OSTI ID: 1564411

Journal Information:: Physica. B, Condensed Matter, Journal Name: Physica. B, Condensed Matter Journal Issue: C Vol. 570; ISSN 0921-4526

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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Related Subjects

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

Data for: Vibrational Properties of Uranium Fluorides Miskowiec, Andrew https://doi.org/10.17632/stdz4yxxsy.1 The current record is supplemented by this dataset	dataset	January 2019
Data for: Vibrational Properties of Uranium Fluorides Miskowiec, Andrew https://doi.org/10.17632/stdz4yxxsy The current record is supplemented by this dataset	dataset	January 2019

Title: Vibrational properties of uranium fluorides

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