DFT+U Study of Chemical Impurities in PuO2

Hernandez, Sarah C.; Holby, Edward F.

doi:10.1021/acs.jpcc.6b03469

DFT+U Study of Chemical Impurities in PuO₂

Journal Article · Tue May 24 00:00:00 EDT 2016 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.6b03469· OSTI ID:1360699

Hernandez, Sarah C. ^[1]; Holby, Edward F. ^[1]

Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

In this paper, we employ density functional theory to explore the effects of impurities in the fluorite crystal structure of PuO₂. The impurities that were considered are known impurities that exist in metallic δ-phase Pu, including H, C, Fe, and Ga. These impurities were placed at various high-symmetry sites within the PuO₂ structure including an octahedral interstitial site, an interstitial site with coordination to two neighboring O atoms, an O substitutional site, and a Pu substitutional site. Incorporation energies were calculated to be energetically unfavorable for all sites except the Pu substitutional site. When impurities were placed in a Pu substitutional site, complexes incorporating the impurities and O formed within the PuO₂ structure. The observed defect-oxygen structures were OH, CO₃, FeO₅, and GaO₃. The presence of these defects led to distortion of the surrounding O atoms within the structure, producing long-range disorder of O atoms. In contrast, perturbations of Pu atoms had a relatively short-range effect on the relaxed structures. These effects are demonstrated via radial distribution functions for O and Pu vacancies. Calculated electronic structure revealed hybridization of the impurity atom with the O valence states and a relative decrease in the Pu 5f states. Minor differences in band gaps were observed for the defected PuO₂ structures containing H, C, and Ga. Finally, Fe-containing structures, however, were calculated to have a significantly decreased band gap, where the implementation of a Hubbard U parameter on the Fe 3d orbitals will maintain the calculated PuO₂ band gap.

View Accepted Manuscript (DOE)

Research Organization:: Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

Sponsoring Organization:: USDOE Laboratory Directed Research and Development (LDRD) Program

Grant/Contract Number:: AC52-06NA25396

OSTI ID:: 1360699

Report Number(s):: LA-UR--16-21938

Journal Information:: Journal of Physical Chemistry. C, Journal Name: Journal of Physical Chemistry. C Journal Issue: 24 Vol. 120; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (39)

Semiempirical GGA-type density functional constructed with a long-range dispersion correction Grimme, Stefan Journal of Computational Chemistry, Vol. 27, Issue 15, p. 1787-1799 https://doi.org/10.1002/jcc.20495	journal	January 2006
Molecular Spectra and Molecular Structure Huber, K. P.; Herzberg, G. https://doi.org/10.1007/978-1-4757-0961-2	book	January 1979
Spectrographic determination of metallic impurities in PuO2 Page, A. G.; Godbole, S. V.; Deshkar, Sandhya Fresenius' Zeitschrift f�r Analytische Chemie, Vol. 287, Issue 4-5 https://doi.org/10.1007/BF00634504	journal	January 1977
Electron beam micro-analysis of some plutonium-iron alloys Scott, V. D. Journal of Nuclear Materials, Vol. 3, Issue 3 https://doi.org/10.1016/0022-3115(61)90196-9	journal	March 1961
The electrical properties of plutonium oxides McNeilly, C. E. Journal of Nuclear Materials, Vol. 11, Issue 1 https://doi.org/10.1016/0022-3115(64)90120-5	journal	January 1964
The plutonium-gallium system Ellinger, F. H.; Land, C. C.; Struebing, V. O. Journal of Nuclear Materials, Vol. 12, Issue 2 https://doi.org/10.1016/0022-3115(64)90145-X	journal	July 1964
Electron microanalysis of gallium and iron in plutonium-gallium and plutonium-iron alloys Harvey, M. R.; Riefenberg, D. H. Journal of Nuclear Materials, Vol. 24, Issue 1 https://doi.org/10.1016/0022-3115(67)90087-6	journal	October 1967
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
Experimental verification of the existence and structure of ζ Pu6Fe in a Pu–Ga alloy Moore, K. T.; Wall, M. A.; Schwartz, A. J. Journal of Nuclear Materials, Vol. 306, Issue 2-3 https://doi.org/10.1016/S0022-3115(02)01319-3	journal	December 2002
Reaction kinetics of plutonium with oxygen, water and humid air: moisture enhancement of the corrosion rate Haschke, John M.; Allen, Thomas H.; Stakebake, Jerry L. Journal of Alloys and Compounds, Vol. 243, Issue 1-2 https://doi.org/10.1016/S0925-8388(96)02328-6	journal	October 1996
Atomic oxygen adsorption on 3.125 at.% Ga stabilized δ-Pu (1 1 1) surface Hernandez, Sarah C.; Venhaus, Thomas J.; Huda, Muhammad N. Journal of Alloys and Compounds, Vol. 643 https://doi.org/10.1016/j.jallcom.2015.04.080	journal	September 2015
Understanding oxygen adsorption on 9.375 at. % Ga-stabilized δ-Pu (111) surface: A DFT study Hernandez, Sarah C.; Wilkerson, Marianne P.; Huda, Muhammad N. Journal of Alloys and Compounds, Vol. 653 https://doi.org/10.1016/j.jallcom.2015.08.246	journal	December 2015
Phase equilibrium of PuO2−x−Pu2O3 based on first-principles calculations and configurational entropy change Minamoto, Satoshi; Kato, Masato; Konashi, Kenji Journal of Nuclear Materials, Vol. 412, Issue 3 https://doi.org/10.1016/j.jnucmat.2011.03.034	journal	May 2011
Characterization and stability of thin oxide films on plutonium surfaces Flores, H. G. García; Roussel, P.; Moore, D. P. Surface Science, Vol. 605, Issue 3-4 https://doi.org/10.1016/j.susc.2010.10.034	journal	February 2011
First-Principles Energetics of Some Nonmetallic Impurity Atoms in Plutonium Dioxide Ao, Bingyun; Lu, Haiyan; Qiu, Ruizhi The Journal of Physical Chemistry C, Vol. 119, Issue 27 https://doi.org/10.1021/acs.jpcc.5b02276	journal	June 2015
Density Functional Theory Studies of the Electronic Structure of Solid State Actinide Oxides Wen, Xiao-Dong; Martin, Richard L.; Henderson, Thomas M. Chemical Reviews, Vol. 113, Issue 2 https://doi.org/10.1021/cr300374y	journal	October 2012
Structural, Energetic, Electronic, Bonding, and Vibrational Properties of Ga ₃ O, Ga ₃ O ₂ , Ga ₃ O ₃ , Ga ₂ O ₃ , and GaO ₃ Clusters Gowtham, S.; Deshpande, Mrinalini; Costales, Aurora The Journal of Physical Chemistry B, Vol. 109, Issue 31 https://doi.org/10.1021/jp050801u	journal	August 2005
Hydrothermal synthesis and structural characterisation of SrFe3(PO4)3(HPO4), an iron(III) phosphate containing FeO5 trigonal bipyramids and dimers of face-sharing FeO6 octahedra Lii, Kwang-Hwa; Dong, Teng-Yuan; Cheng, Chih-Yi Journal of the Chemical Society, Dalton Transactions, Issue 4 https://doi.org/10.1039/dt9930000577	journal	January 1993
First-principles local density approximation+U and generalized gradient approximation+U study of plutonium oxides Sun, Bo; Zhang, Ping; Zhao, Xian-Geng The Journal of Chemical Physics, Vol. 128, Issue 8 https://doi.org/10.1063/1.2833553	journal	February 2008
A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu Grimme, Stefan; Antony, Jens; Ehrlich, Stephan The Journal of Chemical Physics, Vol. 132, Issue 15 https://doi.org/10.1063/1.3382344	journal	April 2010
Effect of spin-orbit coupling on the actinide dioxides AnO ₂ (An=Th, Pa, U, Np, Pu, and Am): A screened hybrid density functional study Wen, Xiao-Dong; Martin, Richard L.; Roy, Lindsay E. The Journal of Chemical Physics, Vol. 137, Issue 15 https://doi.org/10.1063/1.4757615	journal	October 2012
Correlation-induced anomalies and extreme sensitivity in fcc Pu Chen, S. P. Philosophical Magazine, Vol. 89, Issue 22-24 https://doi.org/10.1080/14786430902791755	journal	August 2009
Equilibrium properties of delta-Pu: LDA+ U calculations (LDAequiv local density approximation) Bouchet, J.; Siberchicot, B.; Jollet, F. Journal of Physics: Condensed Matter, Vol. 12, Issue 8 https://doi.org/10.1088/0953-8984/12/8/315	journal	February 2000
Hydrogen trapping in δ-Pu: insights from electronic structure calculations Taylor, Christopher D.; Hernandez, Sarah C.; Francis, Michael F. Journal of Physics: Condensed Matter, Vol. 25, Issue 26 https://doi.org/10.1088/0953-8984/25/26/265001	journal	May 2013
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
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
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
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
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
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
Structural, thermodynamic, and electronic properties of plutonium oxides from first principles Jomard, Gérald; Amadon, Bernard; Bottin, François Physical Review B, Vol. 78, Issue 7 https://doi.org/10.1103/PhysRevB.78.075125	journal	August 2008
Generalized Gradient Approximation Made Simple Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868 https://doi.org/10.1103/PhysRevLett.77.3865	journal	October 1996
Generalized Gradient Approximation Made Simple [Phys. Rev. Lett. 77, 3865 (1996)] Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias Physical Review Letters, Vol. 78, Issue 7 https://doi.org/10.1103/PhysRevLett.78.1396	journal	February 1997
First principle study of the behavior of helium in plutonium dioxide Tian, Xiaofeng; Gao, Tao; Lu, Chunhai The European Physical Journal B, Vol. 86, Issue 4 https://doi.org/10.1140/epjb/e2013-31047-y	journal	April 2013
Ignition Behavior of Plutonium Metal and Certain Binary Alloys Schnizlein, J. G.; Fischer, D. F. Journal of The Electrochemical Society, Vol. 115, Issue 5 https://doi.org/10.1149/1.2411272	journal	January 1968
Handbook of Chemoinformatics Algorithms Faulon, Jean-Loup; Bender, Andreas Chapman and Hall/CRC https://doi.org/10.1201/9781420082999	book	April 2010
“Cathode Region” Method for the Spectrochemical (dc Arc) Determination of Impurities in Plutonium Avni, R.; Boukobza, A.; Daniel, B. Applied Spectroscopy, Vol. 24, Issue 4 https://doi.org/10.1366/000370270774371499	journal	July 1970
Determination of Impurities in Uranium and Plutonium Dioxides by Laser-Induced Breakdown Spectroscopy Fichet, P.; Mauchien, P.; Moulin, C. Applied Spectroscopy, Vol. 53, Issue 9 https://doi.org/10.1366/0003702991947892	journal	September 1999
Hydrogen-Vacancy Effects in Pu-2 at. % Ga Alloys Schwartz, Daniel S.; Richmond, Scott; Smith, Alice I. MRS Proceedings, Vol. 1444 https://doi.org/10.1557/opl.2012.1125	journal	January 2012

Cited By (4)

First-principles study of phase stability, electronic and mechanical properties of plutonium sub-oxides Ghosh, P. S.; Arya, A. Physical Chemistry Chemical Physics, Vol. 21, Issue 30 https://doi.org/10.1039/c9cp01858a	journal	January 2019
A comparative study on modeling of the ferromagnetic and paramagnetic states of uranium hydride using a DFT+ U method Jun, KyuJung; Lee, Jae-Uk; Chang, Min Ho Physical Chemistry Chemical Physics, Vol. 21, Issue 32 https://doi.org/10.1039/c9cp03188j	journal	January 2019
Dependency of f states in fluorite-type XO ₂ (X = Ce, Th, U) on the stability and electronic state of doped transition metals Ding, Qian; Qiu, Ruizhi; Ao, Bingyun Physical Chemistry Chemical Physics, Vol. 21, Issue 47 https://doi.org/10.1039/c9cp04371c	journal	January 2019
Electronic structure of interstitial hydrogen in lutetium oxide from DFT + U calculations and comparison study with μ SR spectroscopy da Silva, E. Lora; Marinopoulos, A. G.; Vieira, R. B. L. Physical Review B, Vol. 94, Issue 1 https://doi.org/10.1103/physrevb.94.014104	journal	July 2016

Similar Records

Local and Nanoscale Structure and Speciation in the PuO{sub 2+x-y}(OH){sub 2y} {center_dot}zH{sub 2}O System

Journal Article · Sun Sep 26 00:00:00 EDT 2004 · Journal of the American Chemical Society · OSTI ID:15016259

Ab initio prediction of rapid kinetics of Fe impurities in δ-Pu

Journal Article · Thu Jun 19 20:00:00 EDT 2025 · Journal of Vacuum Science & Technology A · OSTI ID:2587884

SOME DECOMPOSITION EFFECTS IN PUO$sub 2$ ON SINTERING

Journal Article · Sat Jun 01 00:00:00 EDT 1963 · Journal of Nuclear Materials (Netherlands) · OSTI ID:4681521

Related Subjects

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY