Exploring metastable states in UO2 using hybrid functionals and dynamical mean field theory

Ratcliff, Laura E.; Genovese, Luigi; Park, Hyowon; Littlewood, Peter B.; Lopez-Bezanilla, Alejandro

doi:10.1088/1361-648x/ac3cf1

Title: Exploring metastable states in UO₂ using hybrid functionals and dynamical mean field theory

Abstract

A detailed exploration of the f-atomic orbital occupancy space for UO2 is performed using a first principles approach based on density functional theory (DFT), employing a full hybrid functional within a systematic basis set. Specifically, the PBE0 functional is combined with an occupancy biasing scheme implemented in a wavelet-based algorithm which is adapted to large supercells. The results are compared with previous DFT + U calculations reported in the literature, while dynamical mean field theory is also performed to provide a further base for comparison. This work shows that the computational complexity of the energy landscape of a correlated f-electron oxide is much richer than has previously been demonstrated. The resulting calculations provide evidence of the existence of multiple previously unexplored metastable electronic states of UO₂, including those with energies which are lower than previously reported ground states.

Authors:

^[1];

^[2]; Park, Hyowon ^[3]; Littlewood, Peter B. ^[4];

^[5]

Imperial College London (United Kingdom)
Alternative Energies and Atomic Energy Commission (CEA), Grenoble (France). INAC-SP2m; Univ. Grenoble Alpes (France)
Argonne National Lab. (ANL), Argonne, IL (United States); Univ. of Illinois, Chicago, IL (United States)
Argonne National Lab. (ANL), Argonne, IL (United States); Univ. of Chicago, IL (United States). James Franck Inst.
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

Publication Date:: Wed Dec 15 00:00:00 EST 2021

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

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division; Engineering and Physical Sciences Research Council (EPSRC); USDOE National Nuclear Security Administration (NNSA)

OSTI Identifier:: 1846919

Report Number(s):: LA-UR-21-30127
Journal ID: ISSN 0953-8984

Grant/Contract Number:: 89233218CNA000001; EP/P033253/1; EP/P020194/1

Resource Type:: Accepted Manuscript

Journal Name:: Journal of Physics. Condensed Matter

Additional Journal Information:: Journal Volume: 34; Journal Issue: 9; Journal ID: ISSN 0953-8984

Publisher:: IOP Publishing

Country of Publication:: United States

Language:: English

Subject:: 36 MATERIALS SCIENCE

Citation Formats


                    Ratcliff, Laura E., Genovese, Luigi, Park, Hyowon, Littlewood, Peter B., and Lopez-Bezanilla, Alejandro. Exploring metastable states in UO2 using hybrid functionals and dynamical mean field theory.  United States: N. p., 2021. 
Web.  doi:10.1088/1361-648x/ac3cf1.

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                    Ratcliff, Laura E., Genovese, Luigi, Park, Hyowon, Littlewood, Peter B., & Lopez-Bezanilla, Alejandro. Exploring metastable states in UO2 using hybrid functionals and dynamical mean field theory.  United States.  https://doi.org/10.1088/1361-648x/ac3cf1

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                    Ratcliff, Laura E., Genovese, Luigi, Park, Hyowon, Littlewood, Peter B., and Lopez-Bezanilla, Alejandro. Wed .  
"Exploring metastable states in UO2 using hybrid functionals and dynamical mean field theory".  United States.  https://doi.org/10.1088/1361-648x/ac3cf1.  https://www.osti.gov/servlets/purl/1846919.

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@article{osti_1846919,

  title        = {Exploring metastable states in UO2 using hybrid functionals and dynamical mean field theory},

  author       = {Ratcliff, Laura E. and Genovese, Luigi and Park, Hyowon and Littlewood, Peter B. and Lopez-Bezanilla, Alejandro},

  abstractNote = {A detailed exploration of the f-atomic orbital occupancy space for UO2 is performed using a first principles approach based on density functional theory (DFT), employing a full hybrid functional within a systematic basis set. Specifically, the PBE0 functional is combined with an occupancy biasing scheme implemented in a wavelet-based algorithm which is adapted to large supercells. The results are compared with previous DFT + U calculations reported in the literature, while dynamical mean field theory is also performed to provide a further base for comparison. This work shows that the computational complexity of the energy landscape of a correlated f-electron oxide is much richer than has previously been demonstrated. The resulting calculations provide evidence of the existence of multiple previously unexplored metastable electronic states of UO2, including those with energies which are lower than previously reported ground states.},

  doi          = {10.1088/1361-648x/ac3cf1},

  journal      = {Journal of Physics. Condensed Matter},

  number       = 9,

  volume       = 34,

  place        = {United States},

  year         = {Wed Dec 15 00:00:00 EST 2021},

  month        = {Wed Dec 15 00:00:00 EST 2021}

}

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Title: Exploring metastable states in UO2 using hybrid functionals and dynamical mean field theory

Abstract

Citation Formats

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

Pseudopotentials for H to Kr optimized for gradient-corrected exchange-correlation functionals journal, May 2005

A self-consistent DFT + DMFT scheme in the projector augmented wave method: applications to cerium, Ce 2 O 3 and Pu 2 O 3 with the Hubbard I solver and comparison to DFT + U journal, February 2012

Toward reliable density functional methods without adjustable parameters: The PBE0 model journal, April 1999

γ and β cerium: LDA + U calculations of ground-state parameters journal, April 2008

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Title: Exploring metastable states in UO₂ using hybrid functionals and dynamical mean field theory

Flexibilities of wavelets as a computational basis set for large-scale electronic structure calculations
journal, May 2020

Exact Double Counting in Combining the Dynamical Mean Field Theory and the Density Functional Theory
journal, November 2015

Efficient hybrid density functional calculations in solids: Assessment of the Heyd–Scuseria–Ernzerhof screened Coulomb hybrid functional
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Dispersion in the Mott insulator UO ₂ : A comparison of photoemission spectroscopy and screened hybrid density functional theory
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Advances in first-principles modelling of point defects in UO ₂ : f electron correlations and the issue of local energy minima
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Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
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Pseudopotentials for H to Kr optimized for gradient-corrected exchange-correlation functionals
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A self-consistent DFT + DMFT scheme in the projector augmented wave method: applications to cerium, Ce ₂ O ₃ and Pu ₂ O ₃ with the Hubbard I solver and comparison to DFT + U
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Toward reliable density functional methods without adjustable parameters: The PBE0 model
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$γ$ and $β$ cerium: $LDA + U$ calculations of ground-state parameters
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Commentary: The Materials Project: A materials genome approach to accelerating materials innovation
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Pressure-driven insulator-metal transition in cubic phase UO ₂
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