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Journal of Chemistry
Volume 2015 (2015), Article ID 142510, 8 pages
Research Article

Near Surface Stoichiometry in UO2: A Density Functional Theory Study

1Idaho National Laboratory, Idaho Falls, ID 83415, USA
2University of Florida, Gainesville, FL 32611, USA

Received 5 February 2015; Revised 13 April 2015; Accepted 20 April 2015

Academic Editor: Nuno A. G. Bandeira

Copyright © 2015 Jianguo Yu et al. This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.


The mechanisms of oxygen stoichiometry variation in UO2 at different temperature and oxygen partial pressure are important for understanding the dynamics of microstructure in these crystals. However, very limited experimental studies have been performed to understand the atomic structure of UO2 near surface and defect effects of near surface on stoichiometry in which the system can exchange atoms with the external reservoir. In this study, the near (110) surface relaxation and stoichiometry in UO2 have been studied with density functional theory (DFT) calculations. On the basis of the point-defect model (PDM), a general expression for the near surface stoichiometric variation is derived by using DFT total-energy calculations and atomistic thermodynamics, in an attempt to pin down the mechanisms of oxygen exchange between the gas environment and defected UO2. By using the derived expression, it is observed that, under poor oxygen conditions, the stoichiometry of near surface is switched from hyperstoichiometric at 300 K with a depth around 3 nm to near-stoichiometric at 1000 K and hypostoichiometric at 2000 K. Furthermore, at very poor oxygen concentrations and high temperatures, our results also suggest that the bulk of the UO2 prefers to be hypostoichiometric, although the surface is near-stoichiometric.