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

Materials & Chemistry Group

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

18 Scopus citations

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
State	Published - Oct 1 2019

Funding

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).

Funders	Funder number
National Technical Nuclear Forensics Centre
U.S. Department of Homeland Security
Design History Society
Domestic Nuclear Detection Office
Engineering and Physical Sciences Research Council	EP/G036675, EP/K016288
Royal Society	EP/L000202
Atomic Weapons Establishment

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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.",

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Noncollinear Relativistic DFT + U Calculations of Actinide Dioxide Surfaces

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