Pathway and energetics of xenon migration in uranium dioxide

Using a combination of density functional theory (DFT), classical potentials, molecular dynamics, and nudged elastic band (NEB) calculations, we explore the diffusion of xenon in uranium dioxide (UO2). We compare migration barriers of empirical potentials with DFT by performing NEB calculations and subsequently we use the DFT-validated empirical potentials to calculate vacancy clusters, with and without xenon, to determine the migration path and barrier of xenon in bulk UO2. We find the following: (i) Two empirical potentials out of four tested agree qualitatively with DFT derived energetics for Schottky defect migration; (ii) through the use of molecular dynamics with empirical potentials, we have found a path for the diffusion of xenon-tetravacancy clusters (Xe + 2V(U) + 2V(O)); (iii) this path has an energy barrier significantly lower than previously reported paths by nearly 1 eV; (iv) we examine the physical contributions to the migration pathway and find the barrier is largely electrostatic and that xenon contributes very little to the barrier height; (v) once a uranium vacancy attaches to a xenon-Schottky defect, the resulting xenon-tetravacancy cluster is strongly bound; and (vi) as xenon in a tetravacancy, a xenon-double Schottky defect can diffuse in a concerted manor with a comparable barrier to xenon in a tetravacancy, but two of the oxygen vacancies are only weakly bound to the defect. DOI: 10.1103/PhysRevB.87.104105