The corrosion and oxidation of actinide metals, leading to the formation of metal-oxide surface layers with the catalytic evolution of hydrogen, impacts the management of nuclear materials. Here, the interaction of hydrogen with actinide dioxide (AnO2, An = U, Np, or Pu) (011) surfaces by Hubbard corrected density functional theory (PBEsol+U) has been studied, including spin–orbit interactions and non-collinear 3k anti-ferromagnetic behavior. The actinide dioxides crystalize in the fluorite-type structure, and although the (111) surface dominates the crystal morphology, the (011) surface energetics may lead to more significant interaction with hydrogen. The dissociative adsorption of hydrogen on the UO2 (0.44 eV), NpO2 (−0.47 eV), and PuO2 (−1.71 eV) (011) surfaces has been calculated. It is found that hydrogen dissociates on the PuO2 (011) surface; however, UO2 (011) and NpO2 (011) surfaces are relatively inert. Recombination of hydrogen ions is likely to occur on the UO2 (011) and NpO2 (011) surfaces, whereas hydroxide formation is shown to occur on the PuO2 (011) surface, which distorts the surface structure.
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7 July 2020
Research Article|
July 02 2020
Interaction of hydrogen with actinide dioxide (011) surfaces
James T. Pegg
;
James T. Pegg
a)
1
Department of Chemistry, University College London
, 20 Gordon Street, London WC1H 0AJ, United Kingdom
2
Atomic Weapons Establishment (AWE) Plc
, Aldermaston, Reading, Berkshire RG7 4PR, United Kingdom
a)Author to whom correspondence should be addressed: pegg.james.t@gmail.com
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Ashley E. Shields
;
Ashley E. Shields
3
Oak Ridge National Laboratory
, One Bethel Valley Road, Oak Ridge, Tennessee 37831, USA
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Mark T. Storr
;
Mark T. Storr
2
Atomic Weapons Establishment (AWE) Plc
, Aldermaston, Reading, Berkshire RG7 4PR, United Kingdom
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David O. Scanlon
;
David O. Scanlon
1
Department of Chemistry, University College London
, 20 Gordon Street, London WC1H 0AJ, United Kingdom
4
Diamond Light Source Ltd., Diamond House, Harwell Science and Innovation Campus
, Didcot, Oxfordshire OX11 0DE, United Kingdom
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Nora H. de Leeuw
Nora H. de Leeuw
b)
1
Department of Chemistry, University College London
, 20 Gordon Street, London WC1H 0AJ, United Kingdom
5
School of Chemistry, University of Leeds
, Leeds LS2 9JT, United Kingdom
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a)Author to whom correspondence should be addressed: pegg.james.t@gmail.com
b)
E-mail: n.h.deleeuw@leeds.ac.uk
J. Chem. Phys. 153, 014705 (2020)
Article history
Received:
April 08 2020
Accepted:
June 16 2020
Citation
James T. Pegg, Ashley E. Shields, Mark T. Storr, David O. Scanlon, Nora H. de Leeuw; Interaction of hydrogen with actinide dioxide (011) surfaces. J. Chem. Phys. 7 July 2020; 153 (1): 014705. https://doi.org/10.1063/5.0010200
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