Structure and cation ordering in La2UO6, Ce2UO6, LaUO4, and CeUO4 by first principles calculations

Casillas-Trujillo, Luis; Xu, H.; McMurray, Jake W.; Shin, Dongwon; Baldinozzi, G.; Sickafus, Kurt

doi:10.1016/j.commatsci.2016.05.042

Title: Structure and cation ordering in La₂UO₆, Ce₂UO₆, LaUO₄, and CeUO₄ by first principles calculations

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Abstract

In the present work, we have used density functional theory (DFT) and DFT+U to investigate the crystal structure and phase stability of four model compounds in the Ln₂O₃-UO₂-UO₃ ternary oxide system: La2UO₆, Ce₂UO₆, LaUO₄, CeUO₄, due to the highly-correlated nature of the f-electrons in uranium. We have considered both hypothetical ordered compounds and compounds in which the cations randomly occupy atomic sites in a fluorite-like lattice. We determined that ordered compounds are stable and are energetically favored compared to disordered configurations, though the ordering tendencies are weak. To model and analyze the structures of these complex oxides, we have used supercells based on a layered atomic model. In the layer model, the supercell is composed of alternating planes of anions and cations. We have considered two different ordering motifs for the cations, namely single species (isoatomic) cation layers versus mixed species cation layers. Energy differences between various ordered cationic arrangements were found to be small. This may have implications regarding radiation stability, since cationic arrangements should be able to change under irradiation with little cost in energy.

Authors:

Casillas-Trujillo, Luis ^[1]; Xu, H. ^[1]; McMurray, Jake W. ^[2]; Shin, Dongwon ^[2]; Baldinozzi, G. ^[3]; Sickafus, Kurt ^[1]

Univ. of Tennessee, Knoxville, TN (United States)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
CNRS, Chatenay-Malabry (France)

Publication Date:: Wed Jul 06 00:00:00 EDT 2016

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

Sponsoring Org.:: USDOE Office of Nuclear Energy (NE); USDOE National Nuclear Security Administration (NNSA)

OSTI Identifier:: 1360025

Alternate Identifier(s):: OSTI ID: 1397519

Grant/Contract Number:: AC05-00OR22725; NA0001983; UT-TENN0112

Resource Type:: Accepted Manuscript

Journal Name:: Computational Materials Science

Additional Journal Information:: Journal Volume: 123; Journal ID: ISSN 0927-0256

Publisher:: Elsevier

Country of Publication:: United States

Language:: English

Subject:: 36 MATERIALS SCIENCE

Citation Formats


                    Casillas-Trujillo, Luis, Xu, H., McMurray, Jake W., Shin, Dongwon, Baldinozzi, G., and Sickafus, Kurt. Structure and cation ordering in La2UO6, Ce2UO6, LaUO4, and CeUO4 by first principles calculations.  United States: N. p., 2016. 
Web.  doi:10.1016/j.commatsci.2016.05.042.

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                    Casillas-Trujillo, Luis, Xu, H., McMurray, Jake W., Shin, Dongwon, Baldinozzi, G., & Sickafus, Kurt. Structure and cation ordering in La2UO6, Ce2UO6, LaUO4, and CeUO4 by first principles calculations.  United States.  https://doi.org/10.1016/j.commatsci.2016.05.042

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                    Casillas-Trujillo, Luis, Xu, H., McMurray, Jake W., Shin, Dongwon, Baldinozzi, G., and Sickafus, Kurt. Wed .  
"Structure and cation ordering in La2UO6, Ce2UO6, LaUO4, and CeUO4 by first principles calculations".  United States.  https://doi.org/10.1016/j.commatsci.2016.05.042.  https://www.osti.gov/servlets/purl/1360025.

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@article{osti_1360025,

  title        = {Structure and cation ordering in La2UO6, Ce2UO6, LaUO4, and CeUO4 by first principles calculations},

  author       = {Casillas-Trujillo, Luis and Xu, H. and McMurray, Jake W. and Shin, Dongwon and Baldinozzi, G. and Sickafus, Kurt},

  abstractNote = {In the present work, we have used density functional theory (DFT) and DFT+U to investigate the crystal structure and phase stability of four model compounds in the Ln2O3-UO2-UO3 ternary oxide system: La2UO6, Ce2UO6, LaUO4, CeUO4, due to the highly-correlated nature of the f-electrons in uranium. We have considered both hypothetical ordered compounds and compounds in which the cations randomly occupy atomic sites in a fluorite-like lattice. We determined that ordered compounds are stable and are energetically favored compared to disordered configurations, though the ordering tendencies are weak. To model and analyze the structures of these complex oxides, we have used supercells based on a layered atomic model. In the layer model, the supercell is composed of alternating planes of anions and cations. We have considered two different ordering motifs for the cations, namely single species (isoatomic) cation layers versus mixed species cation layers. Energy differences between various ordered cationic arrangements were found to be small. This may have implications regarding radiation stability, since cationic arrangements should be able to change under irradiation with little cost in energy.},

  doi          = {10.1016/j.commatsci.2016.05.042},

  journal      = {Computational Materials Science},

  number       = ,

  volume       = 123,

  place        = {United States},

  year         = {Wed Jul 06 00:00:00 EDT 2016},

  month        = {Wed Jul 06 00:00:00 EDT 2016}

}

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Title: Structure and cation ordering in La2UO6, Ce2UO6, LaUO4, and CeUO4 by first principles calculations

Abstract

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Title: Structure and cation ordering in La₂UO₆, Ce₂UO₆, LaUO₄, and CeUO₄ by first principles calculations