Impact of anharmonicity on the vibrational entropy and specific heat of
Abstract
The impact of anharmonicity on the vibrational entropy and heat capacity of UO2 has been investigated from 10 K to 1200 K using inelastic neutron scattering measurements of the phonon density of states (PDOS). Small changes in the PDOS are observed from 10 K to 295 K, with more noticeable changes appearing in the 750 K and 1200 K data. The specific heat determined from the PDOS measurements is in agreement with macroscopic specific heat measurements and the overall impact of non-dilation anharmonicity on the specific heat has been shown to be less than 2 percent. An analysis of the phonon measurements shows that the softening of acoustic phonons with temperature is consistent with the quasiharmonic approximation. The optical phonons deviate from the quasiharmonic prediction, with the low energy optical phonons between approximately 20-50 meV softening more than expected, while the higher energy optical phonons between approximately 50-80 meV have no appreciable softening over the temperature range measured. The observation of a small anharmonic specific heat contribution has been shown to be the result of relatively large energy dependent anharmonic effects which have opposite sign, leading to a total contribution near zero.
- Authors:
-
[1];
[1]
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
- Missouri Univ. of Science and Technology, Rolla, MO (United States)
- Idaho National Lab. (INL), Idaho Falls, ID (United States)
- Publication Date:
- Research Org.:
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Idaho National Lab. (INL), Idaho Falls, ID (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1530058
- Alternate Identifier(s):
- OSTI ID: 1546418; OSTI ID: 1558431
- Report Number(s):
- INL/JOU-19-54373-Rev000
Journal ID: ISSN 2475-9953; PRMHAR
- Grant/Contract Number:
- AC05-00OR22725; AC07-05ID14517
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Physical Review Materials
- Additional Journal Information:
- Journal Volume: 3; Journal Issue: 6; Journal ID: ISSN 2475-9953
- Publisher:
- American Physical Society (APS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY; 36 MATERIALS SCIENCE; Specific Heat
Citation Formats
Bryan, M. S., Pang, J. W. L., Larson, B. C., Chernatynskiy, A., Abernathy, D. L., Gofryk, K., and Manley, M. E. Impact of anharmonicity on the vibrational entropy and specific heat of UO2. United States: N. p., 2019.
Web. doi:10.1103/PhysRevMaterials.3.065405.
Bryan, M. S., Pang, J. W. L., Larson, B. C., Chernatynskiy, A., Abernathy, D. L., Gofryk, K., & Manley, M. E. Impact of anharmonicity on the vibrational entropy and specific heat of UO2. United States. doi:10.1103/PhysRevMaterials.3.065405.
Bryan, M. S., Pang, J. W. L., Larson, B. C., Chernatynskiy, A., Abernathy, D. L., Gofryk, K., and Manley, M. E. Fri .
"Impact of anharmonicity on the vibrational entropy and specific heat of UO2". United States. doi:10.1103/PhysRevMaterials.3.065405. https://www.osti.gov/servlets/purl/1530058.
@article{osti_1530058,
title = {Impact of anharmonicity on the vibrational entropy and specific heat of UO2},
author = {Bryan, M. S. and Pang, J. W. L. and Larson, B. C. and Chernatynskiy, A. and Abernathy, D. L. and Gofryk, K. and Manley, M. E.},
abstractNote = {The impact of anharmonicity on the vibrational entropy and heat capacity of UO2 has been investigated from 10 K to 1200 K using inelastic neutron scattering measurements of the phonon density of states (PDOS). Small changes in the PDOS are observed from 10 K to 295 K, with more noticeable changes appearing in the 750 K and 1200 K data. The specific heat determined from the PDOS measurements is in agreement with macroscopic specific heat measurements and the overall impact of non-dilation anharmonicity on the specific heat has been shown to be less than 2 percent. An analysis of the phonon measurements shows that the softening of acoustic phonons with temperature is consistent with the quasiharmonic approximation. The optical phonons deviate from the quasiharmonic prediction, with the low energy optical phonons between approximately 20-50 meV softening more than expected, while the higher energy optical phonons between approximately 50-80 meV have no appreciable softening over the temperature range measured. The observation of a small anharmonic specific heat contribution has been shown to be the result of relatively large energy dependent anharmonic effects which have opposite sign, leading to a total contribution near zero.},
doi = {10.1103/PhysRevMaterials.3.065405},
journal = {Physical Review Materials},
number = 6,
volume = 3,
place = {United States},
year = {2019},
month = {6}
}
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Works referenced in this record:
Phonon Lifetime Investigation of Anharmonicity and Thermal Conductivity of by Neutron Scattering and Theory
journal, April 2013
- Pang, Judy W. L.; Buyers, William J. L.; Chernatynskiy, Aleksandr
- Physical Review Letters, Vol. 110, Issue 15
Origin of Low Thermal Conductivity in Nuclear Fuels
journal, June 2008
- Yin, Quan; Savrasov, Sergey Y.
- Physical Review Letters, Vol. 100, Issue 22
Thermodynamic properties of uranium dioxide: A study of the experimental enthalpy and specific heat
journal, June 1981
- Browning, P.
- Journal of Nuclear Materials, Vol. 98, Issue 3
Anharmonic specific heat of solid UO2
journal, January 1981
- Hyland, G. J.; Stoneham, A. M.
- Journal of Nuclear Materials, Vol. 96, Issue 1-2
The Crystal Dynamics of Uranium Dioxide
journal, August 1965
- Dolling, G.; Cowley, R. A.; Woods, A. D. B.
- Canadian Journal of Physics, Vol. 43, Issue 8
Enthalpy and heat capacity of the actinide oxides
journal, June 1982
- Fink, J. K.
- International Journal of Thermophysics, Vol. 3, Issue 2
Re-analysis of single-crystal neutron-diffraction data on UO2 using third cumulants
journal, July 1980
- Willis, B. T. M.; Hazell, R. G.
- Acta Crystallographica Section A: Crystal Physics, Diffraction, Theoretical and General Crystallography, Vol. 36, Issue 4
Phonon density of states and anharmonicity of
journal, March 2014
- Pang, Judy W. L.; Chernatynskiy, Aleksandr; Larson, Bennett C.
- Physical Review B, Vol. 89, Issue 11
The lattice dynamics of an anharmonic crystal
journal, October 1963
- Cowley, R. A.
- Advances in Physics, Vol. 12, Issue 48
Anharmonic contributions to vibrational thermodynamic properties of solids
journal, September 1961
- Maradudin, A. A.; Flinn, P. A.; Coldwell-Horsfall, R. A.
- Annals of Physics, Vol. 15, Issue 3
Thermodynamics of the UO2+x phase I. Heat capacities of UO2.017 and UO2.254 from 300 to 1000 K and electronic contributions
journal, September 1970
- Grønvold, Fredrik; Kveseth, Nils Jørgen; Sveen, Arvid
- The Journal of Chemical Thermodynamics, Vol. 2, Issue 5
The magnetic transition, heat capacity, and thermodynamic properties of uranium dioxide from 5 to 350 K
journal, January 1971
- Huntzicker, James J.; Westrum, Edgar F.
- The Journal of Chemical Thermodynamics, Vol. 3, Issue 1
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
A radial collimator for a time-of-flight neutron spectrometer
journal, August 2014
- Stone, M. B.; Niedziela, J. L.; Loguillo, M. J.
- Review of Scientific Instruments, Vol. 85, Issue 8
Neutron magnetic form factors of uranium ions
journal, February 1976
- Freeman, A. J.; Desclaux, J. P.; Lander, G. H.
- Physical Review B, Vol. 13, Issue 3
Magnetic moment distribution in uranium monosulphide
journal, September 1972
- Wedgwood, F. A.
- Journal of Physics C: Solid State Physics, Vol. 5, Issue 17
Neutron diffraction study of U : Antiferromagnetic state
journal, August 1976
- Faber, J.; Lander, G. H.
- Physical Review B, Vol. 14, Issue 3
Magnetic Excitations in Uranium Dioxide
journal, March 1968
- Cowley, R. A.; Dolling, G.
- Physical Review, Vol. 167, Issue 2
Multipolar, magnetic, and vibrational lattice dynamics in the low-temperature phase of uranium dioxide
journal, September 2011
- Caciuffo, R.; Santini, P.; Carretta, S.
- Physical Review B, Vol. 84, Issue 10
Magnetic excitations and dynamical Jahn-Teller distortions in
journal, June 1999
- Caciuffo, R.; Amoretti, G.; Santini, P.
- Physical Review B, Vol. 59, Issue 21
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
Neutron scattering lengths and cross sections
journal, January 1992
- Sears, Varley F.
- Neutron News, Vol. 3, Issue 3
Evaluation of thermal properties of UO2 and PuO2 by equilibrium molecular dynamics simulations from 300 to 2000K
journal, September 2005
- Arima, Tatsumi; Yamasaki, Sho; Inagaki, Yaohiro
- Journal of Alloys and Compounds, Vol. 400, Issue 1-2
Fast ion diffusion, superionic conductivity and phase transitions of the nuclear materials UO 2 and Li 2 O
journal, September 2007
- Goel, Prabhatasree; Choudhury, N.; Chaplot, S. L.
- Journal of Physics: Condensed Matter, Vol. 19, Issue 38
Quadrupolar Waves in Uranium Dioxide
journal, October 2010
- Carretta, S.; Santini, P.; Caciuffo, R.
- Physical Review Letters, Vol. 105, Issue 16
The Spin-Wave Dispersion Relations and the Spin-Wave Contribution to the Specific Heat of Antiferromagnetic UO2
journal, January 1969
- Cracknell, A. P.; Joshua, S. J.
- physica status solidi (b), Vol. 36, Issue 2
Thermophysical properties of uranium dioxide
journal, March 2000
- Fink, J. K.
- Journal of Nuclear Materials, Vol. 279, Issue 1
Specific heat of uranium dioxide (UO2) between 0.3 and 50 K
journal, January 1983
- Khattak, G. D.
- Physica Status Solidi (a), Vol. 75, Issue 1
Magnon Contribution to the Low-Temperature Specific Heat of UO2
journal, January 1967
- De Batist, R.; Gevers, R.; Verschueren, M.
- physica status solidi (b), Vol. 19, Issue 1
5 f -electron states in uranium dioxide investigated using high-resolution neutron spectroscopy
journal, July 1989
- Amoretti, G.; Blaise, A.; Caciuffo, R.
- Physical Review B, Vol. 40, Issue 3
Oxidation and crystal field effects in uranium
journal, July 2015
- Tobin, J. G.; Yu, S. -W.; Booth, C. H.
- Physical Review B, Vol. 92, Issue 3
Crystal-field transitions in f -electron oxides
journal, September 1985
- Kern, S.; Loong, C. -K.; Lander, G. H.
- Physical Review B, Vol. 32, Issue 5
Heat capacity measurement of U1−yGdyO2 (0.00 ≦ y ≦ 0.142) from 310 to 1500 K
journal, August 1987
- Inaba, Hideaki; Naito, Keiji; Oguma, Masaomi
- Journal of Nuclear Materials, Vol. 149, Issue 3
Heat Capacity Measurements of U 1-y Gd y O 2 (y=0–0.27)from 325 to 1,673 K
journal, February 2004
- Amaya, Masaki; Une, Katsumi; Hirai, Mutsumi
- Journal of Nuclear Science and Technology, Vol. 41, Issue 2
Quadrupole Polarization in Simulations of Ionic Systems: Application to AgCl
journal, January 1996
- Wilson, Mark; Madden, Paul A.; Costa-Cabral, Benedito J.
- The Journal of Physical Chemistry, Vol. 100, Issue 4
Anisotropic multipolar exchange interactions in systems with strong spin-orbit coupling
journal, July 2014
- Pi, Shu-Ting; Nanguneri, Ravindra; Savrasov, Sergey
- Physical Review B, Vol. 90, Issue 4
Calculation of Multipolar Exchange Interactions in Spin-Orbital Coupled Systems
journal, February 2014
- Pi, Shu-Ting; Nanguneri, Ravindra; Savrasov, Sergey
- Physical Review Letters, Vol. 112, Issue 7
Heat capacity anomaly in UO2 in the vicinity of 1300K: an improved description based on high resolution X-ray and neutron powder diffraction studies
journal, May 2005
- Ruello, P.; Desgranges, L.; Baldinozzi, G.
- Journal of Physics and Chemistry of Solids, Vol. 66, Issue 5
High-temperature studies of UO2 and ThO2 using neutron scattering techniques
journal, January 1987
- Hutchings, Michael T.
- Journal of the Chemical Society, Faraday Transactions 2, Vol. 83, Issue 7
Analysis of recent measurements of the heat capacity of uranium dioxide
journal, October 1994
- Ronchi, C.; Hyland, G. J.
- Journal of Alloys and Compounds, Vol. 213-214
Anharmonic contributions to vibrational thermodynamic properties of solids
journal, September 1961
- Maradudin, A. A.; Flinn, P. A.; Coldwell-Horsfall, R. A.
- Annals of Physics, Vol. 15, Issue 3
Anharmonic contributions to vibrational thermodynamic properties of solids
journal, May 1963
- Flinn, P. A.; Maradudin, A. A.
- Annals of Physics, Vol. 22, Issue 2
Works referencing / citing this record:
Specific heat of uranium dioxide (UO2) between 0.3 and 50 K
journal, January 1983
- Khattak, G. D.
- Physica Status Solidi (a), Vol. 75, Issue 1
Magnon Contribution to the Low-Temperature Specific Heat of UO2
journal, January 1967
- De Batist, R.; Gevers, R.; Verschueren, M.
- physica status solidi (b), Vol. 19, Issue 1
The Spin-Wave Dispersion Relations and the Spin-Wave Contribution to the Specific Heat of Antiferromagnetic UO2
journal, January 1969
- Cracknell, A. P.; Joshua, S. J.
- physica status solidi (b), Vol. 36, Issue 2
Enthalpy and heat capacity of the actinide oxides
journal, June 1982
- Fink, J. K.
- International Journal of Thermophysics, Vol. 3, Issue 2
Anharmonic contributions to vibrational thermodynamic properties of solids
journal, September 1961
- Maradudin, A. A.; Flinn, P. A.; Coldwell-Horsfall, R. A.
- Annals of Physics, Vol. 15, Issue 3
Thermodynamics of the UO2+x phase I. Heat capacities of UO2.017 and UO2.254 from 300 to 1000 K and electronic contributions
journal, September 1970
- Grønvold, Fredrik; Kveseth, Nils Jørgen; Sveen, Arvid
- The Journal of Chemical Thermodynamics, Vol. 2, Issue 5
Thermodynamic properties of uranium dioxide: A study of the experimental enthalpy and specific heat
journal, June 1981
- Browning, P.
- Journal of Nuclear Materials, Vol. 98, Issue 3
Anharmonic specific heat of solid UO2
journal, January 1981
- Hyland, G. J.; Stoneham, A. M.
- Journal of Nuclear Materials, Vol. 96, Issue 1-2
Heat capacity measurement of U1−yGdyO2 (0.00 ≦ y ≦ 0.142) from 310 to 1500 K
journal, August 1987
- Inaba, Hideaki; Naito, Keiji; Oguma, Masaomi
- Journal of Nuclear Materials, Vol. 149, Issue 3
Analysis of recent measurements of the heat capacity of uranium dioxide
journal, October 1994
- Ronchi, C.; Hyland, G. J.
- Journal of Alloys and Compounds, Vol. 213-214
Evaluation of thermal properties of UO2 and PuO2 by equilibrium molecular dynamics simulations from 300 to 2000K
journal, September 2005
- Arima, Tatsumi; Yamasaki, Sho; Inagaki, Yaohiro
- Journal of Alloys and Compounds, Vol. 400, Issue 1-2
Heat capacity anomaly in UO2 in the vicinity of 1300K: an improved description based on high resolution X-ray and neutron powder diffraction studies
journal, May 2005
- Ruello, P.; Desgranges, L.; Baldinozzi, G.
- Journal of Physics and Chemistry of Solids, Vol. 66, Issue 5
The magnetic transition, heat capacity, and thermodynamic properties of uranium dioxide from 5 to 350 K
journal, January 1971
- Huntzicker, James J.; Westrum, Edgar F.
- The Journal of Chemical Thermodynamics, Vol. 3, Issue 1
Thermophysical properties of uranium dioxide
journal, March 2000
- Fink, J. K.
- Journal of Nuclear Materials, Vol. 279, Issue 1
Quadrupole Polarization in Simulations of Ionic Systems: Application to AgCl
journal, January 1996
- Wilson, Mark; Madden, Paul A.; Costa-Cabral, Benedito J.
- The Journal of Physical Chemistry, Vol. 100, Issue 4
High-temperature studies of UO2 and ThO2 using neutron scattering techniques
journal, January 1987
- Hutchings, Michael T.
- Journal of the Chemical Society, Faraday Transactions 2, Vol. 83, Issue 7
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
A radial collimator for a time-of-flight neutron spectrometer
journal, August 2014
- Stone, M. B.; Niedziela, J. L.; Loguillo, M. J.
- Review of Scientific Instruments, Vol. 85, Issue 8
The lattice dynamics of an anharmonic crystal
journal, October 1963
- Cowley, R. A.
- Advances in Physics, Vol. 12, Issue 48
Neutron scattering lengths and cross sections
journal, January 1992
- Sears, Varley F.
- Neutron News, Vol. 3, Issue 3
Heat Capacity Measurements of U 1-y Gd y O 2 (y=0–0.27)from 325 to 1,673 K
journal, February 2004
- Amaya, Masaki; Une, Katsumi; Hirai, Mutsumi
- Journal of Nuclear Science and Technology, Vol. 41, Issue 2
Magnetic moment distribution in uranium monosulphide
journal, September 1972
- Wedgwood, F. A.
- Journal of Physics C: Solid State Physics, Vol. 5, Issue 17
Fast ion diffusion, superionic conductivity and phase transitions of the nuclear materials UO 2 and Li 2 O
journal, September 2007
- Goel, Prabhatasree; Choudhury, N.; Chaplot, S. L.
- Journal of Physics: Condensed Matter, Vol. 19, Issue 38
Magnetic Excitations in Uranium Dioxide
journal, March 1968
- Cowley, R. A.; Dolling, G.
- Physical Review, Vol. 167, Issue 2
Neutron magnetic form factors of uranium ions
journal, February 1976
- Freeman, A. J.; Desclaux, J. P.; Lander, G. H.
- Physical Review B, Vol. 13, Issue 3
Neutron diffraction study of U : Antiferromagnetic state
journal, August 1976
- Faber, J.; Lander, G. H.
- Physical Review B, Vol. 14, Issue 3
Crystal-field transitions in f -electron oxides
journal, September 1985
- Kern, S.; Loong, C. -K.; Lander, G. H.
- Physical Review B, Vol. 32, Issue 5
5 f -electron states in uranium dioxide investigated using high-resolution neutron spectroscopy
journal, July 1989
- Amoretti, G.; Blaise, A.; Caciuffo, R.
- Physical Review B, Vol. 40, Issue 3
Magnetic excitations and dynamical Jahn-Teller distortions in
journal, June 1999
- Caciuffo, R.; Amoretti, G.; Santini, P.
- Physical Review B, Vol. 59, Issue 21
Multipolar, magnetic, and vibrational lattice dynamics in the low-temperature phase of uranium dioxide
journal, September 2011
- Caciuffo, R.; Santini, P.; Carretta, S.
- Physical Review B, Vol. 84, Issue 10
Phonon density of states and anharmonicity of
journal, March 2014
- Pang, Judy W. L.; Chernatynskiy, Aleksandr; Larson, Bennett C.
- Physical Review B, Vol. 89, Issue 11
Anisotropic multipolar exchange interactions in systems with strong spin-orbit coupling
journal, July 2014
- Pi, Shu-Ting; Nanguneri, Ravindra; Savrasov, Sergey
- Physical Review B, Vol. 90, Issue 4
Oxidation and crystal field effects in uranium
journal, July 2015
- Tobin, J. G.; Yu, S. -W.; Booth, C. H.
- Physical Review B, Vol. 92, Issue 3
Origin of Low Thermal Conductivity in Nuclear Fuels
journal, June 2008
- Yin, Quan; Savrasov, Sergey Y.
- Physical Review Letters, Vol. 100, Issue 22
Quadrupolar Waves in Uranium Dioxide
journal, October 2010
- Carretta, S.; Santini, P.; Caciuffo, R.
- Physical Review Letters, Vol. 105, Issue 16
Phonon Lifetime Investigation of Anharmonicity and Thermal Conductivity of by Neutron Scattering and Theory
journal, April 2013
- Pang, Judy W. L.; Buyers, William J. L.; Chernatynskiy, Aleksandr
- Physical Review Letters, Vol. 110, Issue 15
Calculation of Multipolar Exchange Interactions in Spin-Orbital Coupled Systems
journal, February 2014
- Pi, Shu-Ting; Nanguneri, Ravindra; Savrasov, Sergey
- Physical Review Letters, Vol. 112, Issue 7
Re-analysis of single-crystal neutron-diffraction data on UO2 using third cumulants
journal, July 1980
- Willis, B. T. M.; Hazell, R. G.
- Acta Crystallographica Section A: Crystal Physics, Diffraction, Theoretical and General Crystallography, Vol. 36, Issue 4
The Crystal Dynamics of Uranium Dioxide
journal, August 1965
- Dolling, G.; Cowley, R. A.; Woods, A. D. B.
- Canadian Journal of Physics, Vol. 43, Issue 8
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