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 · 24 June 2019 · Physica. B, Condensed Matter

DOI: https://doi.org/10.1016/j.physb.2019.06.049 · OSTI ID:1564411

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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:: 1564411

Alternate ID(s):: OSTI ID: 1542246

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

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

References (62)

Crystal structures of α-UF5 and U2F9 and spectral characterizationof U2F9 Gary Eller, P.; Larson, A. C.; Peterson, J. R. Inorganica Chimica Acta, Vol. 37 https://doi.org/10.1016/S0020-1693(00)95530-0	journal	January 1979
The Crystal Structure of U ₂ F ₉ Zachariasen, W. H. The Journal of Chemical Physics, Vol. 16, Issue 4 https://doi.org/10.1063/1.1746909	journal	April 1948
Temperature variation of the structural parameters in actinide tetrafluorides Kern, S.; Hayward, J.; Roberts, S. The Journal of Chemical Physics, Vol. 101, Issue 11 https://doi.org/10.1063/1.467963	journal	December 1994
Neutron diffraction study of β-uranium pentafluoride between 77 and 403 K Taylor, J. C.; Waugh, A. B. Journal of Solid State Chemistry, Vol. 35, Issue 2 https://doi.org/10.1016/0022-4596(80)90485-5	journal	November 1980
Condensed equilibria in the uranium(III)-uranium(IV) fluoride system Thoma, Roy E.; Insley, Herbert; Brunton, George D. Journal of Inorganic and Nuclear Chemistry, Vol. 36, Issue 5 https://doi.org/10.1016/0022-1902(74)80219-8	journal	May 1974
Crystal chemical studies of the 5 f -series of elements. XI. The crystal structure of α-UF ₅ and of β-UF ₅ Zachariasen, W. H. Acta Crystallographica, Vol. 2, Issue 5 https://doi.org/10.1107/S0365110X4900076X	journal	October 1949
Micro-Raman Spectroscopy of Selected Solid U _x O _y F _z Compounds Armstrong, D. P.; Jarabek, R. J.; Fletcher, W. H. Applied Spectroscopy, Vol. 43, Issue 3 https://doi.org/10.1366/0003702894203002	journal	March 1989
The structures of fluorides X. Neutron powder diffraction profile studies of UF6 at 193°K and 293°K Taylor, J. C.; Wilson, P. W. Journal of Solid State Chemistry, Vol. 14, Issue 4 https://doi.org/10.1016/0022-4596(75)90059-6	journal	August 1975
Characterization of uranium tetrafluoride (UF ₄ ) with Raman spectroscopy : Characterization of UF Villa-Aleman, Eliel; Wellons, Matthew S. Journal of Raman Spectroscopy, Vol. 47, Issue 7 https://doi.org/10.1002/jrs.4909	journal	March 2016
Vibrational spectra of some heavy metal teftafluorides in the solid state Goldstein, M.; Hughes, R. J.; Unsworth, W. D. Spectrochimica Acta Part A: Molecular Spectroscopy, Vol. 31, Issue 5-6 https://doi.org/10.1016/0584-8539(75)80055-9	journal	May 1975
Simulation of Inelastic Neutron Scattering Spectra Using OCLIMAX Cheng, Y. Q.; Daemen, L. L.; Kolesnikov, A. I. Journal of Chemical Theory and Computation, Vol. 15, Issue 3 https://doi.org/10.1021/acs.jctc.8b01250	journal	January 2019
Convenient multigram syntheses of uranium pentafluoride and uranium pentaethoxide Halstead, Gordon W.; Eller, P. Gary; Asprey, Larned B. Inorganic Chemistry, Vol. 17, Issue 10 https://doi.org/10.1021/ic50188a059	journal	October 1978
Nonaqueous chemistry of uranium pentafluoride Halstead, Gordon W.; Eller, P. Gary; Eastman, Michael P. Inorganic Chemistry, Vol. 18, Issue 10 https://doi.org/10.1021/ic50200a047	journal	October 1979
A simple multigram synthesis of β-UF5 - reduction of UF6 by PF3 O'Donnell, T. A.; Rietz, R.; Yeh, S. Journal of Fluorine Chemistry, Vol. 23, Issue 1 https://doi.org/10.1016/S0022-1139(00)81282-8	journal	July 1983
Synthesis, characterization, and structure of uranium oxide tetrafluoride Paine, R. T.; Ryan, R. R.; Asprey, L. B. Inorganic Chemistry, Vol. 14, Issue 5 https://doi.org/10.1021/ic50147a031	journal	May 1975
One-electron reduction synthesis of uranium pentafluoride Asprey, Larmed B.; Paine, Robert T. Journal of the Chemical Society, Chemical Communications, Issue 23 https://doi.org/10.1039/c39730000920	journal	January 1973
VESTA 3 for three-dimensional visualization of crystal, volumetric and morphology data Momma, Koichi; Izumi, Fujio Journal of Applied Crystallography, Vol. 44, Issue 6 https://doi.org/10.1107/S0021889811038970	journal	October 2011
aCLIMAX 4.0.1, The new version of the software for analyzing and interpreting INS spectra Ramirez-Cuesta, A. J. Computer Physics Communications, Vol. 157, Issue 3 https://doi.org/10.1016/S0010-4655(03)00520-4	journal	March 2004
Phonon Lifetime Investigation of Anharmonicity and Thermal Conductivity of UO 2 by Neutron Scattering and Theory Pang, Judy W. L.; Buyers, William J. L.; Chernatynskiy, Aleksandr Physical Review Letters, Vol. 110, Issue 15 https://doi.org/10.1103/PhysRevLett.110.157401	journal	April 2013
Phonon density of states and anharmonicity of UO 2 Pang, Judy W. L.; Chernatynskiy, Aleksandr; Larson, Bennett C. Physical Review B, Vol. 89, Issue 11 https://doi.org/10.1103/PhysRevB.89.115132	journal	March 2014
Measurement of the phonon density of states of PuO 2 ( + 2 % Ga): A critical test of theory Manley, M. E.; Jeffries, J. R.; Said, A. H. Physical Review B, Vol. 85, Issue 13 https://doi.org/10.1103/PhysRevB.85.132301	journal	April 2012
Distributions of phonon lifetimes in Brillouin zones Togo, Atsushi; Chaput, Laurent; Tanaka, Isao Physical Review B, Vol. 91, Issue 9 https://doi.org/10.1103/PhysRevB.91.094306	journal	March 2015
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set Kresse, G.; Furthmüller, J. Physical Review B, Vol. 54, Issue 16, p. 11169-11186 https://doi.org/10.1103/PhysRevB.54.11169	journal	October 1996
Ab initiomolecular dynamics for liquid metals Kresse, G.; Hafner, J. Physical Review B, Vol. 47, Issue 1, p. 558-561 https://doi.org/10.1103/PhysRevB.47.558	journal	January 1993
Projector augmented-wave method Blöchl, P. E. Physical Review B, Vol. 50, Issue 24, p. 17953-17979 https://doi.org/10.1103/PhysRevB.50.17953	journal	December 1994
From ultrasoft pseudopotentials to the projector augmented-wave method Kresse, G.; Joubert, D. Physical Review B, Vol. 59, Issue 3, p. 1758-1775 https://doi.org/10.1103/PhysRevB.59.1758	journal	January 1999
Special points for Brillouin-zone integrations Monkhorst, Hendrik J.; Pack, James D. Physical Review B, Vol. 13, Issue 12, p. 5188-5192 https://doi.org/10.1103/PhysRevB.13.5188	journal	June 1976
High-precision sampling for Brillouin-zone integration in metals Methfessel, M.; Paxton, A. T. Physical Review B, Vol. 40, Issue 6 https://doi.org/10.1103/PhysRevB.40.3616	journal	August 1989
Restoring the Density-Gradient Expansion for Exchange in Solids and Surfaces Perdew, John P.; Ruzsinszky, Adrienn; Csonka, Gábor I. Physical Review Letters, Vol. 100, Issue 13 https://doi.org/10.1103/PhysRevLett.100.136406	journal	April 2008
Electron-energy-loss spectra and the structural stability of nickel oxide: An LSDA+U study Dudarev, S. L.; Botton, G. A.; Savrasov, S. Y. Physical Review B, Vol. 57, Issue 3, p. 1505-1509 https://doi.org/10.1103/PhysRevB.57.1505	journal	January 1998
Benchmarking the DFT+ U Method for Thermochemical Calculations of Uranium Molecular Compounds and Solids Beridze, George; Kowalski, Piotr M. The Journal of Physical Chemistry A, Vol. 118, Issue 50 https://doi.org/10.1021/jp5101126	journal	December 2014
Linear response approach to the calculation of the effective interaction parameters in the LDA + U method Cococcioni, Matteo; de Gironcoli, Stefano Physical Review B, Vol. 71, Issue 3 https://doi.org/10.1103/PhysRevB.71.035105	journal	January 2005
Occupation matrix control of d- and f-electron localisations using DFT + U Allen, Jeremy P.; Watson, Graeme W. Phys. Chem. Chem. Phys., Vol. 16, Issue 39 https://doi.org/10.1039/C4CP01083C	journal	January 2014
Method for locating low-energy solutions within DFT + U Meredig, B.; Thompson, A.; Hansen, H. A. Physical Review B, Vol. 82, Issue 19 https://doi.org/10.1103/PhysRevB.82.195128	journal	November 2010
Phonons and related crystal properties from density-functional perturbation theory Baroni, Stefano; de Gironcoli, Stefano; Dal Corso, Andrea Reviews of Modern Physics, Vol. 73, Issue 2 https://doi.org/10.1103/RevModPhys.73.515	journal	July 2001
Infrared and Raman spectra of disordered materials from first principles Umari, P.; Pasquarello, Alfredo Diamond and Related Materials, Vol. 14, Issue 8 https://doi.org/10.1016/j.diamond.2004.12.007	journal	August 2005
First principles phonon calculations in materials science Togo, Atsushi; Tanaka, Isao Scripta Materialia, Vol. 108 https://doi.org/10.1016/j.scriptamat.2015.07.021	journal	November 2015
Hexafluorides of Molybdenum, Tungsten, and Uranium. I. Reactions with Nitrous and Nitric Oxides Geichman, J. R.; Smith, E. A.; Trond, S. S. Inorganic Chemistry, Vol. 1, Issue 3 https://doi.org/10.1021/ic50003a042	journal	August 1962
Hexafluorides of Molybdenum, Tungsten, and Uranium. II. Reactions with Nitryl Fluoride, Nitrosyl Fluoride, and Nitrosyl Chloride Geichman, J. R.; Smith, E. A.; Ogle, P. R. Inorganic Chemistry, Vol. 2, Issue 5 https://doi.org/10.1021/ic50009a031	journal	October 1963
A rapid and specific titrimetric method for the precise determination of uranium using iron(II) sulphate as reductant Davies, W. Talanta, Vol. 11, Issue 8 https://doi.org/10.1016/0039-9140(64)80171-5	journal	August 1964
GSAS-II : the genesis of a modern open-source all purpose crystallography software package Toby, Brian H.; Von Dreele, Robert B. Journal of Applied Crystallography, Vol. 46, Issue 2 https://doi.org/10.1107/S0021889813003531	journal	March 2013
Design and operation of the wide angular-range chopper spectrometer ARCS at the Spallation Neutron Source Abernathy, D. L.; Stone, M. B.; Loguillo, M. J. Review of Scientific Instruments, Vol. 83, Issue 1 https://doi.org/10.1063/1.3680104	journal	January 2012
Surface degradation of uranium tetrafluoride Tobin, J. G.; Duffin, A. M.; Yu, S. -W. Journal of Vacuum Science & Technology A: Vacuum, Surfaces, and Films, Vol. 35, Issue 3 https://doi.org/10.1116/1.4979540	journal	May 2017
An optical study of α-UF5 and β-UF5 Hecht, H. G.; Malm, J. G.; Carnall, W. T. Journal of the Less Common Metals, Vol. 115, Issue 1 https://doi.org/10.1016/0022-5088(86)90373-5	journal	January 1986
Sintering and Hot Pressing of Uranium Tetrafluoride Barnes, E.; Murray, P. Journal of the American Ceramic Society, Vol. 41, Issue 7 https://doi.org/10.1111/j.1151-2916.1958.tb13549.x	journal	July 1958
Crystallographic parameters in α-UF5 and U2F9 by multiphase refinement of high-resolution neutron powder data Howard, C. J.; Taylor, J. C.; Waugh, A. B. Journal of Solid State Chemistry, Vol. 45, Issue 3 https://doi.org/10.1016/0022-4596(82)90185-2	journal	December 1982
Magnetic susceptibility of uranium trifluoride in the range 2-300.degree.K Berger, Michael; Sienko, Michell J. Inorganic Chemistry, Vol. 6, Issue 2 https://doi.org/10.1021/ic50048a029	journal	February 1967
The Magnetic Susceptibilities of Some Tetravalent Uranium Fluorides Elliott, Norman Physical Review, Vol. 76, Issue 3 https://doi.org/10.1103/PhysRev.76.431.2	journal	August 1949
X-ray photoelectron spectra of the U 4f levels in UF4, UF5 and UF6 Trowbridge, L. D.; Richards, H. L. Surface and Interface Analysis, Vol. 4, Issue 3 https://doi.org/10.1002/sia.740040303	journal	June 1982
A Relation Between Internuclear Distances and Bond Force Constants Badger, Richard M. The Journal of Chemical Physics, Vol. 2, Issue 3 https://doi.org/10.1063/1.1749433	journal	March 1934
Vibrational spectra and force constants of uranium tetrafluoride Krasser, W.; Nürnberg, H. W. Spectrochimica Acta Part A: Molecular Spectroscopy, Vol. 26, Issue 5 https://doi.org/10.1016/0584-8539(70)80008-3	journal	May 1970
Infrared Absorption Spectra of Potassium Uranium Fluorides Soga, T.; Ohwada, K.; Iwasaki, M. Applied Spectroscopy, Vol. 26, Issue 4 https://doi.org/10.1366/000370272774351903	journal	July 1972
Far i.r. spectra of sodium uranium fluorides Ohwada, K.; Soga, T.; Iwasaki, M. Journal of Inorganic and Nuclear Chemistry, Vol. 34, Issue 1 https://doi.org/10.1016/0022-1902(72)80402-0	journal	January 1972
Beitr�ge zur Chemie der Uranfluoride und -oxidfluoride. II. Darstellung und Schwingungsspektren von ?- und ?-Uranpentafluorid Jacob, E. Zeitschrift f�r anorganische und allgemeine Chemie, Vol. 400, Issue 1 https://doi.org/10.1002/zaac.19734000107	journal	August 1973
Systematic features in the structural chemistry of the uranium halides, oxyhalides and related transition metal and lanthanide halides Taylor, J. C. Coordination Chemistry Reviews, Vol. 20, Issue 3 https://doi.org/10.1016/S0010-8545(00)80325-2	journal	September 1976
Vibrational thermodynamics of materials Fultz, Brent Progress in Materials Science, Vol. 55, Issue 4 https://doi.org/10.1016/j.pmatsci.2009.05.002	journal	May 2010
Connection between the true vibrational density of states and that derived from inelastic neutron scattering Taraskin, S. N.; Elliott, S. R. Physical Review B, Vol. 55, Issue 1 https://doi.org/10.1103/PhysRevB.55.117	journal	January 1997
Efficient procedure for the evaluation of multiple scattering and multiphonon corrections in inelastic neutron-scattering experiments Dawidowski, J.; Bermejo, F. J.; Granada, J. R. Physical Review B, Vol. 58, Issue 2 https://doi.org/10.1103/PhysRevB.58.706	journal	July 1998
Mantid—Data analysis and visualization package for neutron scattering and μ SR experiments Arnold, O.; Bilheux, J. C.; Borreguero, J. M. Nuclear Instruments and Methods in Physics Research Section A: Accelerators, Spectrometers, Detectors and Associated Equipment, Vol. 764 https://doi.org/10.1016/j.nima.2014.07.029	journal	November 2014
Neutron scattering measurements of phonons in nickel at elevated temperatures Kresch, M.; Delaire, O.; Stevens, R. Physical Review B, Vol. 75, Issue 10 https://doi.org/10.1103/PhysRevB.75.104301	journal	March 2007
Multiphonon: Phonon Density of States tools for Inelastic Neutron Scattering Powder Data Y. Y. Lin, Jiao; Islam, Fahima; Kresh, Max The Journal of Open Source Software, Vol. 3, Issue 21 https://doi.org/10.21105/joss.00440	journal	January 2018
Actual and Idealized Crystal Field Parameterizations for the Uranium Ions in UF4 Gajek, Z.; Mulak, J.; Krupa, J. C. Journal of Solid State Chemistry, Vol. 107, Issue 2 https://doi.org/10.1006/jssc.1993.1366	journal	December 1993

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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 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.1 The current record is supplemented by this dataset	dataset	January 2019

Title: Vibrational properties of uranium fluorides

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