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Water Adsorption on AnO2 {111}, {110}, and {100} Surfaces (An = U and Pu): A Density Functional Theory + U Study

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School of Chemistry, The University of Manchester, Oxford Road, Manchester M13 9PL, United Kingdom
Department of Chemistry, University of Bath, Claverton Down, Bath BA2 7AY, United Kingdom
§ Department of Chemistry, University of Huddersfield, Queensgate, Huddersfield HD1 3DH, United Kingdom
Department of Chemistry, Lancaster University, Bailrigg, Lancaster LA1 4YB, United Kingdom
Cite this: J. Phys. Chem. C 2017, 121, 3, 1675–1682
Publication Date (Web):December 22, 2016
https://doi.org/10.1021/acs.jpcc.6b10986
Copyright © 2016 American Chemical Society

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    Abstract

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    The interactions between water and the actinide oxides UO2 and PuO2 are important both fundamentally and when considering the long-term storage of spent nuclear fuel. However, experimental studies in this area are severely limited by the intense radioactivity of plutonium, and hence, we have recently begun to investigate these interactions computationally. In this paper, we report the results of plane-wave density functional theory calculations of the interaction of water with the {111}, {110}, and {100} surfaces of UO2 and PuO2, using a Hubbard-corrected potential (PBE + U) approach to account for the strongly correlated 5f electrons. We find a mix of molecular and dissociative water adsorption to be most stable on the {111} surface, whereas the fully dissociative water adsorption is most stable on the {110} and {100} surfaces, leading to a fully hydroxylated monolayer. From these results, we derive water desorption temperatures at various pressures for the different surfaces. These increase in the order {111} < {110} < {100}, and these data are used to propose an alternative interpretation for the two experimentally determined temperature ranges for water desorption from PuO2.

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    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.jpcc.6b10986.

    • Calculated desorption temperatures from AnO2 {111}, {110}, and {100} surfaces (An = U and Pu) at various pressures (Tables S1–S6) and ball-and-stick representations of the geometries of all of the stable adsorption structures (Figures S1–S56) (PDF)

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