First-principles calculations of oxygen interstitials in corundum: a site symmetry approach

Abstract

Using site symmetry analysis, four possible positions of interstitial oxygen atoms in the α-Al₂O₃ hexagonal structure have been identified and studied. First principles hybrid functional calculations of the relevant atomic and electronic structures for interstitial O_i atom insertion in these positions reveal differences in energies of ∼1.5 eV. This approach allows us to get the lowest energy configuration, avoiding time-consuming calculations. It is shown that the triplet oxygen atom is barrierless displaced towards the nearest regular oxygen ion, forming a singlet dumbbell (split interstitial) configuration with an energy gain of ∼2.5 eV. The charge and spatial structure of the dumbbell is discussed. Our results are important, in particular, for understanding the radiation properties and stability of α-Al₂O₃ and other oxide crystals.