Noncollinear Relativistic DFT + U Calculations of Actinide Dioxide Surfaces

James T. Pegg; Ashley E. Shields; Mark T. Storr; David O. Scanlon; Nora H. De Leeuw

doi:10.1021/acs.jpcc.8b07823

Noncollinear Relativistic DFT + U Calculations of Actinide Dioxide Surfaces

James T. Pegg^*, Ashley E. Shields, Mark T. Storr, David O. Scanlon, Nora H. De Leeuw

^*Corresponding author for this work

Chemistry

Research output: Contribution to journal › Article › peer-review

Abstract

A noncollinear relativistic PBEsol + U study of low-index actinide dioxides (AnO₂, An = U, Np, or Pu) surfaces has been conducted. The importance of magnetic vector reorientation relative to the plane of the surface is highlighted; this has often been ignored in collinear nonrelativistic models. The use of noncollinear relativistic methods is key to the design of reliable computational models. The ionic relaxation of each surface is shown to be confined to the first three monolayers, and we have explored the configurations of the terminal oxygen ions on the reconstructed (001) surface. The reconstructed (001) surfaces are ordered as (001)αβ < (001)α < (001)β in terms of energetics. Electrostatic potential isosurface and scanning tunneling microscopy images have also been calculated. By considering the energetics of the low-index AnO₂ surfaces, an octahedral Wulff crystal morphology has been calculated.

Original language	English
Pages (from-to)	356-366
Number of pages	11
Journal	Journal of Physical Chemistry C
Volume	123
Issue number	1
DOIs	https://doi.org/10.1021/acs.jpcc.8b07823
Publication status	Published - 1 Oct 2019

Bibliographical note

Funding Information:
This research was supported by the UK Engineering & Physical Science Research Council (EPSRC) (grant nos. EP/G036675 and EP/K016288) and the Atomic Weapons Establishment Ltd (AWE). A.E.S. gratefully acknowledges the United States Department of Homeland Security (DHS), Domestic Nuclear Detection Office (DNDO), and National Technical Nuclear Forensics Centre (NTNFC) for a postdoctoral research fellowship. N.H.d.L. thanks the Royal Society for an industry fellowship and AWE for a William Penney fellowship. This work made use of the ARCHER UK National Supercomputing Service (http://www.archer.ac.uk) via our membership of the UK’s HEC Materials Chemistry Consortium, which is funded by EPSRC (EP/L000202).

Publisher Copyright:
© 2018 American Chemical Society.

ASJC Scopus subject areas

Electronic, Optical and Magnetic Materials
General Energy
Physical and Theoretical Chemistry
Surfaces, Coatings and Films

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10.1021/acs.jpcc.8b07823

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abstract = "A noncollinear relativistic PBEsol + U study of low-index actinide dioxides (AnO2, An = U, Np, or Pu) surfaces has been conducted. The importance of magnetic vector reorientation relative to the plane of the surface is highlighted; this has often been ignored in collinear nonrelativistic models. The use of noncollinear relativistic methods is key to the design of reliable computational models. The ionic relaxation of each surface is shown to be confined to the first three monolayers, and we have explored the configurations of the terminal oxygen ions on the reconstructed (001) surface. The reconstructed (001) surfaces are ordered as (001)αβ < (001)α < (001)β in terms of energetics. Electrostatic potential isosurface and scanning tunneling microscopy images have also been calculated. By considering the energetics of the low-index AnO2 surfaces, an octahedral Wulff crystal morphology has been calculated.",

author = "Pegg, {James T.} and Shields, {Ashley E.} and Storr, {Mark T.} and Scanlon, {David O.} and {De Leeuw}, {Nora H.}",

note = "Funding Information: This research was supported by the UK Engineering & Physical Science Research Council (EPSRC) (grant nos. EP/G036675 and EP/K016288) and the Atomic Weapons Establishment Ltd (AWE). A.E.S. gratefully acknowledges the United States Department of Homeland Security (DHS), Domestic Nuclear Detection Office (DNDO), and National Technical Nuclear Forensics Centre (NTNFC) for a postdoctoral research fellowship. N.H.d.L. thanks the Royal Society for an industry fellowship and AWE for a William Penney fellowship. This work made use of the ARCHER UK National Supercomputing Service (http://www.archer.ac.uk) via our membership of the UK{\textquoteright}s HEC Materials Chemistry Consortium, which is funded by EPSRC (EP/L000202). Publisher Copyright: {\textcopyright} 2018 American Chemical Society.",

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Noncollinear Relativistic DFT + U Calculations of Actinide Dioxide Surfaces

Abstract

Bibliographical note

ASJC Scopus subject areas

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