The interaction of atomic and molecular hydrogen with actinide dioxide (AnO2, 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 UO2 (0.82 eV), NpO2 (−0.10 eV), and PuO2 (−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 AnO2 (111) surfaces is favoured over hydroxide formation.
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7 April 2019
Research Article|
April 01 2019
Interaction of hydrogen with actinide dioxide (111) 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 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 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
5
Thomas Young Centre, University College London
, Gower Street, London WC1E 6BT, United Kingdom
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Nora H. de Leeuw
Nora H. de Leeuw
1
Department of Chemistry, University College London
, 20 Gordon Street, London WC1H 0AJ, United Kingdom
6
School of Chemistry, Cardiff University
, Main Building, Park Place, Cardiff CF1D 3AT, United Kingdom
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a)Author to whom correspondence should be addressed: pegg.james.t@gmail.com
J. Chem. Phys. 150, 134701 (2019)
Article history
Received:
January 02 2019
Accepted:
March 03 2019
Citation
James T. Pegg, Ashley E. Shields, Mark T. Storr, David O. Scanlon, Nora H. de Leeuw; Interaction of hydrogen with actinide dioxide (111) surfaces. J. Chem. Phys. 7 April 2019; 150 (13): 134701. https://doi.org/10.1063/1.5087577
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