Interaction of hydrogen with actinide dioxide (111) surfaces

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

doi:10.1063/1.5087577

Interaction of hydrogen with actinide dioxide (111) 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

9 Scopus citations

Abstract

The interaction of atomic and molecular hydrogen with actinide dioxide (AnO ₂ , An = U, Np, Pu) (111) surfaces has been investigated by DFT+U, where noncollinear 3k antiferromagnetic behaviour and spin-orbit interactions are considered. The adsorption of atomic hydrogen forms a hydroxide group, coupled to the reduction of an actinide ion. The energy of atomic hydrogen adsorption on the UO ₂ (0.82 eV), NpO ₂ (−0.10 eV), and PuO ₂ (−1.25 eV) surfaces has been calculated. The dissociation of molecular hydrogen is not observed, shown to be due to kinetic rather than thermodynamic factors. As a barrier to the formation of a second hydroxyl group, an unusual charge distribution has been shown. This could be a limitation of a (1·1) unit cell method or an artefact of the systems. The recombination of hydrogen ions on the AnO ₂ (111) surfaces is favoured over hydroxide formation.

Original language	English
Article number	134701
Journal	Journal of Chemical Physics
Volume	150
Issue number	13
DOIs	https://doi.org/10.1063/1.5087577
State	Published - Apr 7 2019

Funding

This research was supported by the UK Engineering and Physical Science Research Council (EPSRC) (Grant Nos. EP/G036675 and EP/K016288) and the Atomic Weapons Establishment (AWE). A.E.S. gratefully acknowledges the United States Department of Homeland Security (DHS), Domestic Nuclear Detection Office (DNDO), 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 (Grant No. 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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title = "Interaction of hydrogen with actinide dioxide (111) surfaces",

abstract = " The interaction of atomic and molecular hydrogen with actinide dioxide (AnO 2 , An = U, Np, Pu) (111) surfaces has been investigated by DFT+U, where noncollinear 3k antiferromagnetic behaviour and spin-orbit interactions are considered. The adsorption of atomic hydrogen forms a hydroxide group, coupled to the reduction of an actinide ion. The energy of atomic hydrogen adsorption on the UO 2 (0.82 eV), NpO 2 (−0.10 eV), and PuO 2 (−1.25 eV) surfaces has been calculated. The dissociation of molecular hydrogen is not observed, shown to be due to kinetic rather than thermodynamic factors. As a barrier to the formation of a second hydroxyl group, an unusual charge distribution has been shown. This could be a limitation of a (1·1) unit cell method or an artefact of the systems. The recombination of hydrogen ions on the AnO 2 (111) surfaces is favoured over hydroxide formation.",

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AU - Pegg, James T.

AU - Shields, Ashley E.

AU - Storr, Mark T.

AU - Scanlon, David O.

AU - De Leeuw, Nora H.

PY - 2019/4/7

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N2 - The interaction of atomic and molecular hydrogen with actinide dioxide (AnO 2 , An = U, Np, Pu) (111) surfaces has been investigated by DFT+U, where noncollinear 3k antiferromagnetic behaviour and spin-orbit interactions are considered. The adsorption of atomic hydrogen forms a hydroxide group, coupled to the reduction of an actinide ion. The energy of atomic hydrogen adsorption on the UO 2 (0.82 eV), NpO 2 (−0.10 eV), and PuO 2 (−1.25 eV) surfaces has been calculated. The dissociation of molecular hydrogen is not observed, shown to be due to kinetic rather than thermodynamic factors. As a barrier to the formation of a second hydroxyl group, an unusual charge distribution has been shown. This could be a limitation of a (1·1) unit cell method or an artefact of the systems. The recombination of hydrogen ions on the AnO 2 (111) surfaces is favoured over hydroxide formation.

AB - The interaction of atomic and molecular hydrogen with actinide dioxide (AnO 2 , An = U, Np, Pu) (111) surfaces has been investigated by DFT+U, where noncollinear 3k antiferromagnetic behaviour and spin-orbit interactions are considered. The adsorption of atomic hydrogen forms a hydroxide group, coupled to the reduction of an actinide ion. The energy of atomic hydrogen adsorption on the UO 2 (0.82 eV), NpO 2 (−0.10 eV), and PuO 2 (−1.25 eV) surfaces has been calculated. The dissociation of molecular hydrogen is not observed, shown to be due to kinetic rather than thermodynamic factors. As a barrier to the formation of a second hydroxyl group, an unusual charge distribution has been shown. This could be a limitation of a (1·1) unit cell method or an artefact of the systems. The recombination of hydrogen ions on the AnO 2 (111) surfaces is favoured over hydroxide formation.

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Interaction of hydrogen with actinide dioxide (111) surfaces

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