Theory of He trapping, diffusion, and clustering in UO2

We have performed ab initio total energy calculations to investigate the behavior of helium and its diffusion properties in uranium dioxide (UO2). Our investigations are based on the density functional theory within the generalized gradient approximation (GGA). The trapping behavior of He in UO2 has been modeled with a supercell containing 96-atoms as well as uranium and oxygen vacancy trapping sites. The calculated incorporation energies show that for He a uranium vacancy is more stable than an oxygen vacancy or an octahedral interstitial site (OIS). Interstitial site hopping is found to be the rate-determining mechanism of the He diffusion process and the corresponding migration energy is computed as 2.79 eV at 0 K (with the spin-orbit coupling (SOC) included), and as 2.09 eV by using the thermally expanded lattice parameter of UO2 at 1200 K, which is relatively close to the experimental value of 2.0 eV. The lattice expansion coefficient of He-induced swelling of UO2 is calculated as 9 × 10−2. For two He atoms, we have found that they form a dumbbell configuration if they are close enough to each other, and that the lattice expansion induced by a dumbbell is larger than by two distant interstitial He atoms. The clustering tendency of He has been studied for small clusters of up to six He atoms. We find that He strongly tends to cluster in the vicinity of an OIS, and that the collective action of the He atoms is sufficient to spontaneously create additional point defects around the He cluster in the UO2 lattice.