Rights statement: This document is the Accepted Manuscript version of a Published Work that appeared in final form in The Journal of Physical Chemistry C, copyright ©2017 American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://pubs.acs.org/doi/abs/10.1021/acs.jpcc.6b10986
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Research output: Contribution to Journal/Magazine › Journal article › peer-review
Research output: Contribution to Journal/Magazine › Journal article › peer-review
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TY - JOUR
T1 - Water Adsorption on AnO 2 {111}, {110} and {100} Surfaces (An = U, Pu); A DFT+U Study
AU - Tegner, Bengt
AU - Molinari, Marco
AU - Kerridge, Andrew
AU - Parker, SC
AU - Kaltsoyannis, Nikolas
N1 - This document is the Accepted Manuscript version of a Published Work that appeared in final form in The Journal of Physical Chemistry C, copyright ©2017 American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://pubs.acs.org/doi/abs/10.1021/acs.jpcc.6b10986
PY - 2017/1/26
Y1 - 2017/1/26
N2 - 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.
AB - 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.
U2 - 10.1021/acs.jpcc.6b10986
DO - 10.1021/acs.jpcc.6b10986
M3 - Journal article
VL - 121
SP - 1675
EP - 1682
JO - The Journal of Physical Chemistry C
JF - The Journal of Physical Chemistry C
SN - 1932-7447
IS - 3
ER -