Vibrational properties of uranium fluorides
Abstract
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) aremore »
- Authors:
- Publication Date:
- Research Org.:
- Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
- Sponsoring Org.:
- USDOE
- OSTI Identifier:
- 1564411
- Alternate Identifier(s):
- OSTI ID: 1542246
- Grant/Contract Number:
- AC05-00OR22725
- Resource Type:
- Published Article
- Journal Name:
- Physica. B, Condensed Matter
- Additional Journal Information:
- Journal Name: Physica. B, Condensed Matter Journal Volume: 570 Journal Issue: C; Journal ID: ISSN 0921-4526
- Publisher:
- Elsevier
- Country of Publication:
- Netherlands
- Language:
- English
- Subject:
- 75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY; Uranium; Phonons; Density functional theory; Inelastic neutron scattering; Lattice dynamics
Citation Formats
Miskowiec, Andrew, Shields, Ashley E., Niedziela, J. L., Cheng, Yongqiang, Taylor, Paul, DelCul, Guillermo, Hunt, Rodney, Spencer, Barry, Langford, John, and Abernathy, Douglas. Vibrational properties of uranium fluorides. Netherlands: N. p., 2019.
Web. doi:10.1016/j.physb.2019.06.049.
Miskowiec, Andrew, Shields, Ashley E., Niedziela, J. L., Cheng, Yongqiang, Taylor, Paul, DelCul, Guillermo, Hunt, Rodney, Spencer, Barry, Langford, John, & Abernathy, Douglas. Vibrational properties of uranium fluorides. Netherlands. https://doi.org/10.1016/j.physb.2019.06.049
Miskowiec, Andrew, Shields, Ashley E., Niedziela, J. L., Cheng, Yongqiang, Taylor, Paul, DelCul, Guillermo, Hunt, Rodney, Spencer, Barry, Langford, John, and Abernathy, Douglas. Tue .
"Vibrational properties of uranium fluorides". Netherlands. https://doi.org/10.1016/j.physb.2019.06.049.
@article{osti_1564411,
title = {Vibrational properties of uranium fluorides},
author = {Miskowiec, Andrew and Shields, Ashley E. and Niedziela, J. L. and Cheng, Yongqiang and Taylor, Paul and DelCul, Guillermo and Hunt, Rodney and Spencer, Barry and Langford, John and Abernathy, Douglas},
abstractNote = {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.},
doi = {10.1016/j.physb.2019.06.049},
journal = {Physica. B, Condensed Matter},
number = C,
volume = 570,
place = {Netherlands},
year = {Tue Oct 01 00:00:00 EDT 2019},
month = {Tue Oct 01 00:00:00 EDT 2019}
}
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Cited by: 4 works
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Figures / Tables:
Fig. 1: Structure of (a) UF3 [2], (b) UF4 [4], (c) U2F9 [3], and (d) 1× 1×2 supercell of β-UF5 [5]. Crystal structure visualizations are produced with VESTA [18].
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