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Title: Analysis of Water Coupling in Inelastic Neutron Spectra of Uranyl Fluoride

Abstract

Inelastic neutron scattering (INS) is uniquely sensitive to hydrogen due to its comparatively large thermal neutron scattering cross-section (82 b). Consequently, the inclusion of water in real samples presents significant challenges to INS data analysis due directly to the scattering strength of hydrogen. Here, we investigate uranyl fluoride (UO2F2) with inelastic neutron scattering. UO2F2 is the hydrolysis product of uranium hexafluoride (UF6), and is a hygroscopic, uranyl-ion containing particulate. Raman spectral signatures are commonly used for inferential understanding of the chemical environment for the uranyl ion in UO2F2, but no direct measurement of the influence of absorbed water molecules on the overall lattice dynamics has been performed until now. To deconvolute the influence of waters on the observed INS spectra, we use density functional theory with full spectral modeling to separate lattice motion from water coupling. In particular, we present a careful and novel analysis of the Q-dependent Debye–Waller factor, allowing us to separate spectral contributions by mass, which reveals preferential water coupling to the uranyl stretching vibrations. Coupled with the detailed partial phonon densities of states calculated via DFT, we infer the probable adsorption locations of interlayer waters. We explain that a common spectral feature in Raman spectra ofmore » uranyl fluoride originates from the interaction of water molecules with the uranyl ion based on this analysis. In conclusion, the Debye–Waller analysis is applicable to all INS spectra and could be used to identify light element contributions in other systems.« less

Authors:
ORCiD logo [1]; ORCiD logo [1];  [2]; ORCiD logo [1]
  1. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Univ. of Tennessee, Knoxville, TN (United States)
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1545232
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
Scientific Reports
Additional Journal Information:
Journal Volume: 9; Journal Issue: 1; Journal ID: ISSN 2045-2322
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY

Citation Formats

Miskowiec, Andrew, Niedziela, Jennifer L., Kirkegaard, Marie C., and Shields, Ashley E. Analysis of Water Coupling in Inelastic Neutron Spectra of Uranyl Fluoride. United States: N. p., 2019. Web. https://doi.org/10.1038/s41598-019-46675-x.
Miskowiec, Andrew, Niedziela, Jennifer L., Kirkegaard, Marie C., & Shields, Ashley E. Analysis of Water Coupling in Inelastic Neutron Spectra of Uranyl Fluoride. United States. https://doi.org/10.1038/s41598-019-46675-x
Miskowiec, Andrew, Niedziela, Jennifer L., Kirkegaard, Marie C., and Shields, Ashley E. Fri . "Analysis of Water Coupling in Inelastic Neutron Spectra of Uranyl Fluoride". United States. https://doi.org/10.1038/s41598-019-46675-x. https://www.osti.gov/servlets/purl/1545232.
@article{osti_1545232,
title = {Analysis of Water Coupling in Inelastic Neutron Spectra of Uranyl Fluoride},
author = {Miskowiec, Andrew and Niedziela, Jennifer L. and Kirkegaard, Marie C. and Shields, Ashley E.},
abstractNote = {Inelastic neutron scattering (INS) is uniquely sensitive to hydrogen due to its comparatively large thermal neutron scattering cross-section (82 b). Consequently, the inclusion of water in real samples presents significant challenges to INS data analysis due directly to the scattering strength of hydrogen. Here, we investigate uranyl fluoride (UO2F2) with inelastic neutron scattering. UO2F2 is the hydrolysis product of uranium hexafluoride (UF6), and is a hygroscopic, uranyl-ion containing particulate. Raman spectral signatures are commonly used for inferential understanding of the chemical environment for the uranyl ion in UO2F2, but no direct measurement of the influence of absorbed water molecules on the overall lattice dynamics has been performed until now. To deconvolute the influence of waters on the observed INS spectra, we use density functional theory with full spectral modeling to separate lattice motion from water coupling. In particular, we present a careful and novel analysis of the Q-dependent Debye–Waller factor, allowing us to separate spectral contributions by mass, which reveals preferential water coupling to the uranyl stretching vibrations. Coupled with the detailed partial phonon densities of states calculated via DFT, we infer the probable adsorption locations of interlayer waters. We explain that a common spectral feature in Raman spectra of uranyl fluoride originates from the interaction of water molecules with the uranyl ion based on this analysis. In conclusion, the Debye–Waller analysis is applicable to all INS spectra and could be used to identify light element contributions in other systems.},
doi = {10.1038/s41598-019-46675-x},
journal = {Scientific Reports},
number = 1,
volume = 9,
place = {United States},
year = {2019},
month = {7}
}

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Works referenced in this record:

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Van der Waals density functionals applied to solids
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Molecular structure of the uranyl mineral andersonite—a Raman spectroscopic study
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Study of the dehydration process of uranyl difluoride hydrates stable under usual conditions of temperature, pressure and atmospheric moisture
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Raman spectroscopic study of the multi-anion uranyl mineral schroeckingerite
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Characterization of Uranium Oxides Using in Situ Micro-Raman Spectroscopy
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Structural Phase Transitions and Water Dynamics in Uranyl Fluoride Hydrates
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Correlation of O-H stretching frequencies and O-H…O hydrogen bond lengths in minerals
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Connection between the true vibrational density of states and that derived from inelastic neutron scattering
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Ab initio molecular-dynamics simulation of the liquid-metal–amorphous-semiconductor transition in germanium
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Chemical accuracy for the van der Waals density functional
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Electron-energy-loss spectra and the structural stability of nickel oxide: An LSDA+U study
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Orbitally driven giant phonon anharmonicity in SnSe
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Simulation of Inelastic Neutron Scattering Spectra Using OCLIMAX
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Vibrational properties of water molecules adsorbed in different zeolitic frameworks
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  • Anisimov, Vladimir I.; Zaanen, Jan; Andersen, Ole K.
  • Physical Review B, Vol. 44, Issue 3, p. 943-954
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Multiphonon: Phonon Density of States tools for Inelastic Neutron Scattering Powder Data
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Van der Waals Density Functional for General Geometries
journal, June 2004


Design and operation of the wide angular-range chopper spectrometer ARCS at the Spallation Neutron Source
journal, January 2012

  • Abernathy, D. L.; Stone, M. B.; Loguillo, M. J.
  • Review of Scientific Instruments, Vol. 83, Issue 1
  • DOI: 10.1063/1.3680104

Role of Lone-Pair Electrons in Producing Minimum Thermal Conductivity in Nitrogen-Group Chalcogenide Compounds
journal, November 2011


Raman spectroscopy of uranium compounds and the use of multivariate analysis for visualization and classification
journal, June 2015


Vibrational thermodynamics of materials
journal, May 2010


Spectroscopic Raman characterization of rutherfordine: a combined DFT and experimental study
journal, January 2016

  • Bonales, L. J.; Colmenero, F.; Cobos, J.
  • Physical Chemistry Chemical Physics, Vol. 18, Issue 24
  • DOI: 10.1039/c6cp01510g

Ab initiomolecular dynamics for liquid metals
journal, January 1993


Efficient Implementation of a van der Waals Density Functional: Application to Double-Wall Carbon Nanotubes
journal, August 2009


Decomposition of Uranyl Fluoride between 700° and 950°C
journal, January 1960

  • Ferris, L. M.; Baird, F. G.
  • Journal of The Electrochemical Society, Vol. 107, Issue 4
  • DOI: 10.1149/1.2427685

Evidence of a Nonphotochemical Mechanism for the Solid-State Formation of Uranyl Peroxide
journal, May 2018


Debye-Waller factors in a quasicrystal
journal, December 2000


Electronic Structure, Spectra, and Magnetic Properties of Oxycations. III. Ligation Effects on the Infrared Spectrum of the Uranyl Ion
journal, July 1961

  • McGlynn, S. P.; Smith, J. K.; Neely, W. C.
  • The Journal of Chemical Physics, Vol. 35, Issue 1
  • DOI: 10.1063/1.1731876

Improved tetrahedron method for Brillouin-zone integrations
journal, June 1994


Combined SEM/EDX and micro-Raman spectroscopy analysis of uranium minerals from a former uranium mine
journal, August 2009


An inelastic incoherent neutron scattering study of water in small-pored zeolites and other water-bearing minerals
journal, May 2000

  • Line, Christina M. B.; Kearley, G. J.
  • The Journal of Chemical Physics, Vol. 112, Issue 20
  • DOI: 10.1063/1.481518

    Works referencing / citing this record:

    A Raman spectroscopic study of the uranyl carbonate rutherfordine
    journal, January 2007

    • Frost, Ray L.; Čejka, Jiří
    • Journal of Raman Spectroscopy, Vol. 38, Issue 11
    • DOI: 10.1002/jrs.1796

    Raman spectroscopic study of the multi-anion uranyl mineral schroeckingerite
    journal, January 2007

    • Frost, Ray L.; Čejka, Jiří; Ayoko, Godwin A.
    • Journal of Raman Spectroscopy, Vol. 38, Issue 12
    • DOI: 10.1002/jrs.1827

    Correlation of O-H stretching frequencies and O-H…O hydrogen bond lengths in minerals
    journal, August 1999

    • Libowitzky, Engen
    • Monatshefte für Chemie / Chemical Monthly, Vol. 130, Issue 8
    • DOI: 10.1007/bf03354882

    Assessing hand-held Raman spectrometer FirstDefender RM for nuclear safeguards applications
    journal, May 2015

    • Berlizov, A.; Ho, D. M. L.; Nicholl, A.
    • Journal of Radioanalytical and Nuclear Chemistry, Vol. 307, Issue 1
    • DOI: 10.1007/s10967-015-4160-z

    The frequency of the HOH bending fundamental in solids and liquids
    journal, January 1984


    Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
    journal, July 1996


    Raman spectroscopy of uranium compounds and the use of multivariate analysis for visualization and classification
    journal, June 2015


    Combined SEM/EDX and micro-Raman spectroscopy analysis of uranium minerals from a former uranium mine
    journal, August 2009


    Molecular structure of the uranyl mineral andersonite—a Raman spectroscopic study
    journal, October 2004


    Mantid—Data analysis and visualization package for neutron scattering and μ SR experiments
    journal, November 2014

    • 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
    • DOI: 10.1016/j.nima.2014.07.029

    Vibrational thermodynamics of materials
    journal, May 2010


    First principles phonon calculations in materials science
    journal, November 2015


    Study of the dehydration process of uranyl difluoride hydrates stable under usual conditions of temperature, pressure and atmospheric moisture
    journal, August 1998


    Evidence of a Nonphotochemical Mechanism for the Solid-State Formation of Uranyl Peroxide
    journal, May 2018


    Simulation of Inelastic Neutron Scattering Spectra Using OCLIMAX
    journal, January 2019

    • Cheng, Y. Q.; Daemen, L. L.; Kolesnikov, A. I.
    • Journal of Chemical Theory and Computation, Vol. 15, Issue 3
    • DOI: 10.1021/acs.jctc.8b01250

    Structural Phase Transitions and Water Dynamics in Uranyl Fluoride Hydrates
    journal, November 2015

    • Miskowiec, Andrew; Kirkegaard, Marie C.; Huq, Ashfia
    • The Journal of Physical Chemistry A, Vol. 119, Issue 49
    • DOI: 10.1021/acs.jpca.5b09296

    Uranium-Oxygen Bond Lengths in Uranyl Salts: Uranyl Fluoride and Uranyl Carbonate.
    journal, June 1963


    Localized vibrational modes in metallic solids
    journal, October 1998

    • Keppens, V.; Mandrus, D.; Sales, B. C.
    • Nature, Vol. 395, Issue 6705
    • DOI: 10.1038/27625

    Orbitally driven giant phonon anharmonicity in SnSe
    journal, October 2015

    • Li, C. W.; Hong, J.; May, A. F.
    • Nature Physics, Vol. 11, Issue 12
    • DOI: 10.1038/nphys3492

    Spectroscopic Raman characterization of rutherfordine: a combined DFT and experimental study
    journal, January 2016

    • Bonales, L. J.; Colmenero, F.; Cobos, J.
    • Physical Chemistry Chemical Physics, Vol. 18, Issue 24
    • DOI: 10.1039/c6cp01510g

    Raman and infrared spectroscopic studies of the uranyl ion: the symmetric stretching frequency, force constants, and bond lengths
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    • Bullock, J. I.
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    Electronic Structure, Spectra, and Magnetic Properties of Oxycations. III. Ligation Effects on the Infrared Spectrum of the Uranyl Ion
    journal, July 1961

    • McGlynn, S. P.; Smith, J. K.; Neely, W. C.
    • The Journal of Chemical Physics, Vol. 35, Issue 1
    • DOI: 10.1063/1.1731876

    Design and operation of the wide angular-range chopper spectrometer ARCS at the Spallation Neutron Source
    journal, January 2012

    • Abernathy, D. L.; Stone, M. B.; Loguillo, M. J.
    • Review of Scientific Instruments, Vol. 83, Issue 1
    • DOI: 10.1063/1.3680104

    An inelastic incoherent neutron scattering study of water in small-pored zeolites and other water-bearing minerals
    journal, May 2000

    • Line, Christina M. B.; Kearley, G. J.
    • The Journal of Chemical Physics, Vol. 112, Issue 20
    • DOI: 10.1063/1.481518

    Vibrational properties of anhydrous and partially hydrated uranyl fluoride
    journal, January 2017

    • Kirkegaard, M. C.; Langford, J.; Steill, J.
    • The Journal of Chemical Physics, Vol. 146, Issue 2
    • DOI: 10.1063/1.4973430

    Time-dependent water dynamics in hydrated uranyl fluoride
    journal, September 2015


    Vibrational properties of water molecules adsorbed in different zeolitic frameworks
    journal, March 2006


    Chemical accuracy for the van der Waals density functional
    journal, December 2009

    • Klimeš, Jiří; Bowler, David R.; Michaelides, Angelos
    • Journal of Physics: Condensed Matter, Vol. 22, Issue 2
    • DOI: 10.1088/0953-8984/22/2/022201

    Band theory and Mott insulators: Hubbard U instead of Stoner I
    journal, July 1991

    • Anisimov, Vladimir I.; Zaanen, Jan; Andersen, Ole K.
    • Physical Review B, Vol. 44, Issue 3, p. 943-954
    • DOI: 10.1103/physrevb.44.943

    Ab initiomolecular dynamics for liquid metals
    journal, January 1993


    Ab initio molecular-dynamics simulation of the liquid-metal–amorphous-semiconductor transition in germanium
    journal, May 1994


    Improved tetrahedron method for Brillouin-zone integrations
    journal, June 1994


    Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
    journal, October 1996


    Connection between the true vibrational density of states and that derived from inelastic neutron scattering
    journal, January 1997


    Electron-energy-loss spectra and the structural stability of nickel oxide: An LSDA+U study
    journal, January 1998

    • Dudarev, S. L.; Botton, G. A.; Savrasov, S. Y.
    • Physical Review B, Vol. 57, Issue 3, p. 1505-1509
    • DOI: 10.1103/physrevb.57.1505

    Debye-Waller factors in a quasicrystal
    journal, December 2000


    Neutron scattering measurements of phonons in nickel at elevated temperatures
    journal, March 2007


    Van der Waals density functionals applied to solids
    journal, May 2011


    Efficient Implementation of a van der Waals Density Functional: Application to Double-Wall Carbon Nanotubes
    journal, August 2009


    Role of Lone-Pair Electrons in Producing Minimum Thermal Conductivity in Nitrogen-Group Chalcogenide Compounds
    journal, November 2011


    Van der Waals Density Functional for General Geometries
    journal, June 2004


    Decomposition of Uranyl Fluoride between 700° and 950°C
    journal, January 1960

    • Ferris, L. M.; Baird, F. G.
    • Journal of The Electrochemical Society, Vol. 107, Issue 4
    • DOI: 10.1149/1.2427685

    Characterization of Uranium Oxides Using in Situ Micro-Raman Spectroscopy
    journal, September 2000


    Micro-Raman Spectroscopy of Selected Solid U x O y F z Compounds
    journal, March 1989

    • Armstrong, D. P.; Jarabek, R. J.; Fletcher, W. H.
    • Applied Spectroscopy, Vol. 43, Issue 3
    • DOI: 10.1366/0003702894203002

    Multiphonon: Phonon Density of States tools for Inelastic Neutron Scattering Powder Data
    journal, January 2018

    • Y. Y. Lin, Jiao; Islam, Fahima; Kresh, Max
    • The Journal of Open Source Software, Vol. 3, Issue 21
    • DOI: 10.21105/joss.00440