Unexpected features in the optical vibrational spectra of δ-UO3

Spano, Tyler L.; Shields, Ashley E.; Niedziela, Jennifer L.; Miskowiec, Andrew

doi:10.3389/fnuen.2022.995292

Title: Unexpected features in the optical vibrational spectra of δ-UO₃

Journal Article · Mon Oct 31 00:00:00 EDT 2022 · Frontiers in Nuclear Engineering

DOI:https://doi.org/10.3389/fnuen.2022.995292· OSTI ID:1896999

^[1];

^[1]

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

Uranium trioxide displays a complex chemical phase space, with at least six structurally distinct polymorphs accessible via different synthetic routes. Remarkably, despite its technological importance, full structural and electronic characterization of these polymorphs remains an open area of study. δ-UO₃ in particular has attracted significant theoretical attention due to its high point group and space group symmetries, having U (VI) in octahedral coordination with polyhedra interconnected through corner-sharing to build a 3-D cubic lattice with space group symmetry Pm-3m and Z = 1. Critical experimental information, such as its optical vibrational spectra, are not known. Here, we study the Raman and infrared (IR) spectra of δ-UO₃ together with the support of density functional theory (DFT) calculations for spectral interpretation. A symmetry analysis of the DFT-predicted phonon eigenmodes indicates that δ-UO₃ should have two IR active modes and no Raman active modes. Experimental results, however, indicate significant Raman scattering from δ-UO₃. We therefore propose four potential explanations for this apparent contradiction: a possible tetragonal distortion to the cubic cell, the existence of a surface impurity layer, vacancy scattering, and structural activation of Raman signal. We use powder X-ray diffraction and confocal Raman spectroscopy with depth profiling to investigate these possibilities and suggest future experiments to explore this phenomenon in more detail. Understanding the lattice dynamics of δ-UO₃ is important for identification of technogenic U phases via Raman and infrared spectroscopy and our results indicate that the simple understanding of δ-UO₃ as a high-symmetry cubic structure should be reconsidered.

View Accepted Manuscript (DOE)

Cite

Export

Save

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

Sponsoring Organization:: USDOE

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 1896999

Journal Information:: Frontiers in Nuclear Engineering, Vol. 1, Issue 1; ISSN 2813-3412

Publisher:: Frontiers Media S.A.Copyright Statement

Country of Publication:: United States

Language:: English

References (28)

Size–strain line-broadening analysis of the ceria round-robin sample Balzar, D.; Audebrand, N.; Daymond, M. R. Journal of Applied Crystallography, Vol. 37, Issue 6 https://doi.org/10.1107/s0021889804022551	journal	November 2004
Determination of the Insulation Gap of Uranium Oxides by Spectroscopic Ellipsometry and Density Functional Theory He, Heming; Andersson, David A.; Allred, David D. The Journal of Physical Chemistry C, Vol. 117, Issue 32 https://doi.org/10.1021/jp401149m	journal	August 2013
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set Kresse, G.; Furthmüller, J. Computational Materials Science, Vol. 6, Issue 1, p. 15-50 https://doi.org/10.1016/0927-0256(96)00008-0	journal	July 1996
A Perfect Smoother Eilers, Paul H. C. Analytical Chemistry, Vol. 75, Issue 14 https://doi.org/10.1021/ac034173t	journal	July 2003
Oxidation kinetics for conversion of U3O8 to ε-UO3 with NO2 Johnson, J. A.; Rawn, C. J.; Spencer, B. B. Journal of Nuclear Materials, Vol. 490 https://doi.org/10.1016/j.jnucmat.2017.03.048	journal	July 2017
Theoretical modeling of the uranium 4f XPS for U(VI) and U(IV) oxides Bagus, Paul S.; Nelin, Connie J.; Ilton, Eugene S. The Journal of Chemical Physics, Vol. 139, Issue 24 https://doi.org/10.1063/1.4846135	journal	December 2013
Scherrer after sixty years: A survey and some new results in the determination of crystallite size Langford, J. I.; Wilson, A. J. C. Journal of Applied Crystallography, Vol. 11, Issue 2 https://doi.org/10.1107/s0021889878012844	journal	April 1978
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
Fityk : a general-purpose peak fitting program Wojdyr, Marcin Journal of Applied Crystallography, Vol. 43, Issue 5 https://doi.org/10.1107/s0021889810030499	journal	September 2010
Preparation of Uranium Trioxide Sheft, Irving; Fried, Sherman; Davidson, Norman Journal of the American Chemical Society, Vol. 72, Issue 5 https://doi.org/10.1021/ja01161a082	journal	May 1950
Thermodynamic studies of studtite thermal decomposition pathways via amorphous intermediates UO3, U2O7, and UO4 Guo, Xiaofeng; Wu, Di; Xu, Hongwu Journal of Nuclear Materials, Vol. 478 https://doi.org/10.1016/j.jnucmat.2016.06.014	journal	September 2016
On the determination of uraniumoxygen bond lengths in dioxouranium(VI) compounds by Raman spectroscopy Bartlett, John R.; Cooney, Ralph P. Journal of Molecular Structure, Vol. 193 https://doi.org/10.1016/0022-2860(89)80140-1	journal	February 1989
Universal link between the boson peak and transverse phonons in glass Shintani, Hiroshi; Tanaka, Hajime Nature Materials, Vol. 7, Issue 11 https://doi.org/10.1038/nmat2293	journal	October 2008
Optical vibrational spectra and proposed crystal structure of ε-UO3 Spano, Tyler L.; Hunt, Rodney; Kapsimalis, Roger J. Journal of Nuclear Materials, Vol. 559 https://doi.org/10.1016/j.jnucmat.2021.153386	journal	February 2022
Computationally Guided Investigation of the Optical Spectra of Pure β-UO ₃ Spano, Tyler L.; Shields, Ashley E.; Barth, Brianna S. Inorganic Chemistry, Vol. 59, Issue 16 https://doi.org/10.1021/acs.inorgchem.0c01279	journal	July 2020
Density Functional Theory Study of the Thermodynamic and Raman Vibrational Properties of γ-UO ₃ Polymorph Colmenero, Francisco; Bonales, Laura. J.; Cobos, Joaquín The Journal of Physical Chemistry C, Vol. 121, Issue 27 https://doi.org/10.1021/acs.jpcc.7b04389	journal	June 2017
Generalized gradient approximation for the exchange-correlation hole of a many-electron system Perdew, John P.; Burke, Kieron; Wang, Yue Physical Review B, Vol. 54, Issue 23 https://doi.org/10.1103/physrevb.54.16533	journal	December 1996
Ab initio molecular-dynamics simulation of the liquid-metal–amorphous-semiconductor transition in germanium Kresse, G.; Hafner, J. Physical Review B, Vol. 49, Issue 20, p. 14251-14269 https://doi.org/10.1103/physrevb.49.14251	journal	May 1994
On the structure of α-UO3 Loopstra, B. O.; Cordfunke, E. H. P. Recueil des Travaux Chimiques des Pays-Bas, Vol. 85, Issue 2 https://doi.org/10.1002/recl.19660850204	journal	January 1966
Structural Properties of Lanthanide and Actinide Compounds within the Plane Wave Pseudopotential Approach Pickard, Chris J.; Winkler, Björn; Chen, Roger K. Physical Review Letters, Vol. 85, Issue 24 https://doi.org/10.1103/physrevlett.85.5122	journal	December 2000
Surface characterisation of α-, β-, γ-, and δ-UO₃using X-ray photoelectron spectroscopy Allen, Geoffrey C.; Holmes, Nigel R. J. Chem. Soc., Dalton Trans., Issue 12 https://doi.org/10.1039/dt9870003009	journal	January 1987
The uranium-oxygen system: U3O8-UO3 Hoekstra, H. R.; Siegel, S. Journal of Inorganic and Nuclear Chemistry, Vol. 18 https://doi.org/10.1016/0022-1902(61)80383-7	journal	March 1961
Ab Initio Investigation of the UO ₃ Polymorphs: Structural Properties and Thermodynamic Stability Brincat, Nicholas A.; Parker, Stephen C.; Molinari, Marco Inorganic Chemistry, Vol. 53, Issue 23 https://doi.org/10.1021/ic500791m	journal	November 2014
First-principles study on oxidation effects in uranium oxides and high-pressure high-temperature behavior of point defects in uranium dioxide Geng, Hua Y.; Song, Hong X.; Jin, K. Physical Review B, Vol. 84, Issue 17 https://doi.org/10.1103/physrevb.84.174115	journal	November 2011
The Scherrer Formula for X-Ray Particle Size Determination Patterson, A. L. Physical Review, Vol. 56, Issue 10 https://doi.org/10.1103/physrev.56.978	journal	November 1939
The structure of δ-UO3 Weller, M. T.; Dickens, P. G.; Penny, D. J. Polyhedron, Vol. 7, Issue 3 https://doi.org/10.1016/s0277-5387(00)80559-8	journal	January 1988
Comparison of bonding and charge density in $δ − U O_{3}, γ − U O_{3}$ , and $L a_{6} U O_{12}$ Casillas-Trujillo, L.; Baldinozzi, G.; Patel, M. K. Physical Review Materials, Vol. 1, Issue 6 https://doi.org/10.1103/physrevmaterials.1.065404	journal	November 2017
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

Similar Records

Combined experimental and theoretical assessments of the lattice dynamics and optoelectronics of TaON and Ta{sub 3}N{sub 5}

Journal Article · Tue Sep 15 00:00:00 EDT 2015 · Journal of Solid State Chemistry · OSTI ID:1896999

Nurlaela, Ela; Harb, Moussab; Gobbo, Silvano del; +2 more

Optical vibrational spectra and proposed crystal structure of ε-UO₃

Journal Article · Thu Nov 18 00:00:00 EST 2021 · Journal of Nuclear Materials · OSTI ID:1896999

Spano, Tyler L.; Hunt, Rodney Dale; Kapsimalis, Roger J.; +3 more

Polymorphic Phase Transition in Superhydrous Phase B

Journal Article · Sat Jan 01 00:00:00 EST 2005 · Phys. Chem. Miner. · OSTI ID:1896999

Koch-Muller, M; Dera, P; Fei, Y; +4 more

Related Subjects

98 NUCLEAR DISARMAMENT, SAFEGUARDS, AND PHYSICAL PROTECTION
δ-UO3
UO3 polymorphs
uranium trioxide
UO3 Raman spectroscopy
UO3 synthesis

Title: Unexpected features in the optical vibrational spectra of δ-UO3

Citation Formats

References (28)

Similar Records

Related Subjects

Title: Unexpected features in the optical vibrational spectra of δ-UO₃