Ab initio modelling of defects in oxides

Two materials, magnesium oxide and magnesium aluminate spinel, have been studied using the ab initio methodology, density functional theory. In the case of MgO, energetics of a variety of point defects were considered. These defects were isolated Schottky and Frenkel defects and interstitial pairs, along with a number of Schottky defects and di-interstitials. Comparisons were made between the density functional theory results and results obtained from empirical potential simulations and these generally showed good agreement. Both methodologies predicted the first nearest neighbour Schottky defects to be the most energetically favourable of the considered Schottky defects and that the first, second, and fifth nearest neighbour di-interstitials were of similar energy and were favoured over the other di-interstitial configurations. Relaxed structures of the defects were analysed, which showed that empirical potential simulations were accurately predicting the displacements of atoms surrounding di-interstitials, but overestimated O atom displacement for Schottky defects. [Continues.

Ab-initio modelling of defects in MgO

The energetics of the key defects that are observed to occur during simulations of radiation damage in MgO are analysed using density functional theory. The results are compared with those from the empirical potentials used to carry out the radiation damage studies. The formation energies of vacancies, interstitials, Frenkel pairs, di-vacancies and di-interstitials are calculated as a function of the increasing supercell size in order to ensure good convergence. The supercell geometries were chosen to maximise the separation distance between periodic images. Their sizes ranged from cells containing 32 atoms up to cells containing 180 atoms. Results are presented for the formation energies of the first, second and third nearest neighbour defects. Results show that the di-vacancy formation energy is in the region of 4–6 eV and that formation energies for di-interstitials are more than double this, lying in the range 12–16 eV. Comparison of the results show that empirical potentials overestimate the formation energy of di-vacancies by 1–3 eV and underestimate the formation energies of di-interstitials by about 1–2 eV. The relative stability of the defects is, however, correctly predicted by the empirical potentials. The direction and the magnitude of the displacements of the atoms surrounding the defects are in good agreement for all the systems containing interstitials. For the systems containing vacancies the direction of the displacements are in agreement but the empirical potentials predict larger displacements in all cases

Ab initio study of point defects in magnesium oxide

Energetics of a variety of point defects in MgO have been considered from an ab initio perspective using density functional theory. The considered defects are isolated Schottky and Frenkel defects and interstitial pairs, along with a number of Schottky defects and di-interstitials. Comparisons were made between the density functional theory results and results obtained from empirical potential simulations and these generally showed good agreement. Both methodologies predicted the first nearest neighbor Schottky defects to be the most energetically favorable of the considered Schottky defects and that the first, second, and fifth nearest neighbor di-interstitials were of similar energy and were favored over the other di-interstitial configurations. Relaxed structures of the defects were analyzed, which showed that empirical potential simulations were accurately predicting the displacements of atoms surrounding di-interstitials, but were overestimating O atom displacement for Schottky defects. Transition barriers were computed for the defects using the nudged elastic band method. Vacancies and Schottky defects were found to have relatively high energy barriers, the majority of which were over 2 eV, in agreement with conclusions reached using empirical potentials. The lowest barriers for di-interstitial transitions were found to be for migration into a first nearest neighbor configuration. Charges were calculated using a Bader analysis and this found negligible charge transfer during the defect transitions and only small changes in the charges on atoms surrounding defects, indicating why fixed charge models work as well as they do

A theoretical study of intrinsic point defects and defect clusters in magnesium aluminate spinel

Point and small cluster defects in magnesium aluminate spinel have been studied from a first principles viewpoint. Typical point defects that occur during collision cascade simulations are cation anti-site defects, which have a small formation energy and are very stable, O and Mg split interstitials and vacancies. Isolated Al interstitials were found to be energetically unfavourable but could occur as part of a split Mg-Al pair or as a three atom-three vacancy Al ‘ring’ defect, previously observed in collision cascades using empirical potentials. The structure and energetics of the defects were investigated using density functional theory (DFT) and the results compared to simulations using empirical fixed-charge potentials. Each point defect was studied in a variety of supercell sizes in order to ensure convergence. It was found that empirical potential simulations significantly overestimate formation energies, but that the type and relative stability of the defects are well-predicted by the empirical potentials both for point defects and small defect clusters