Water adsorption on AnO2 {111}, {110}, and {100} surfaces (An = U and Pu): A density functional theory + U study

Bengt E. Tegner, Marco Molinari, Andrew Kerridge, Stephen C. Parker, Nikolas Kaltsoyannis

Research output: Contribution to journalArticle

18 Citations (Scopus)

Abstract

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. (Figure Presented).

LanguageEnglish
Pages1675-1682
Number of pages8
JournalJournal of Physical Chemistry C
Volume121
Issue number3
Early online date22 Dec 2016
DOIs
Publication statusPublished - 26 Jan 2017

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Density functional theory
density functional theory
Adsorption
adsorption
Water
water
Desorption
desorption
Actinoid Series Elements
Plutonium
spent fuels
nuclear fuels
Actinides
Spent fuels
plutonium
Radioactivity
Nuclear fuels
interactions
radioactivity
Oxides

Cite this

Tegner, Bengt E. ; Molinari, Marco ; Kerridge, Andrew ; Parker, Stephen C. ; Kaltsoyannis, Nikolas. / Water adsorption on AnO2 {111}, {110}, and {100} surfaces (An = U and Pu) : A density functional theory + U study. In: Journal of Physical Chemistry C. 2017 ; Vol. 121, No. 3. pp. 1675-1682.
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Water adsorption on AnO2 {111}, {110}, and {100} surfaces (An = U and Pu) : A density functional theory + U study. / Tegner, Bengt E.; Molinari, Marco; Kerridge, Andrew; Parker, Stephen C.; Kaltsoyannis, Nikolas.

In: Journal of Physical Chemistry C, Vol. 121, No. 3, 26.01.2017, p. 1675-1682.

Research output: Contribution to journalArticle

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