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Solid State Ionics, Vol.266, 68-72, 2014
Vacancy mediated cation migration in uranium dioxide: The influence of cluster configuration
The effect of cluster configuration on vacancy mediated uranium migration is investigated for stoichiometric UO2 and hyper-stoichiometric UO2+x. The minimum enthalpy pathway involves reconfiguration of the most stable cluster to a metastable configuration, in stoichiometric and hyper-stoichiometric systems. Additionally, a much larger number of alternative metastable configurations were identified for UO2+x, compared to UO2. This would lead to a larger contribution to the Arrhenius pre-exponential term with hyper-stoichiometry. Consequently, the often made assumption that re-orientation of the ground state cluster offers access to the migration activation energy cannot be assumed to be valid. Crown Copyright (C) 2014 Published by Elsevier B.V. All rights reserved.
Keywords:Defect migration;Atomic scale simulation;Uranium dioxide;Metastable clusters;Ionic defect cluster morphology