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

^*Corresponding author for this work

Chemistry

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

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
Publication status	Published - 7 Apr 2019

Bibliographical note

Funding Information:
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).

Publisher Copyright:
© 2019 Crown.

ASJC Scopus subject areas

General Physics and Astronomy
Physical and Theoretical Chemistry

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10.1063/1.5087577

Cite this

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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.",

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 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{\textquoteright}s HEC Materials Chemistry Consortium, which is funded by EPSRC (Grant No. EP/L000202). Publisher Copyright: {\textcopyright} 2019 Crown.",

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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.

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Interaction of hydrogen with actinide dioxide (111) surfaces

Abstract

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