Importance of elastic finite-size effects: neutral defects in ionic compounds

TL;DR

This paper demonstrates that elastic finite-size effects significantly impact defect calculations in ionic compounds, challenging previous assumptions and highlighting the need for larger supercells to avoid misinterpretation of defect structures.

Contribution

It reveals that elastic effects, not just electrostatic ones, are crucial in defect modeling of ionic materials and introduces methods to assess these effects.

Findings

Elastic effects cause errors in small supercell defect calculations.

Larger supercells eliminate the misidentification of defect structures.

Elastic self-interaction is present across various ionic compounds and methods.

Abstract

Small system sizes are a well known source of error in DFT calculations, yet computational constraints frequently dictate the use of small supercells, often as small as 96 atoms in oxides and compound semiconductors. In ionic compounds, electrostatic finite size effects have been well characterised, but self-interaction of charge neutral defects is often discounted or assumed to follow an asymptotic behaviour and thus easily corrected with linear elastic theory. Here we show that elastic effects are also important in the description of defects in ionic compounds and can lead to qualitatively incorrect conclusions if inadequately small supercells are used; moreover, the spurious self-interaction does not follow the behaviour predicted by linear elastic theory. Considering the exemplar cases of metal oxides with fluorite structure, we show that numerous previous studies, employing 96-atom supercells, misidentify the ground state structure of (charge neutral) Schottky defects. We show that the error is eliminated by employing larger cells (324, 768 and 1500 atoms), and careful analysis determines that elastic effects, not electrostatic, are responsible. The spurious self-interaction was also observed in non-oxide ionic compounds and irrespective of the computational method used, thereby resolving long standing discrepancies between DFT and force-field methods, previously attributed to the level of theory. The surprising magnitude of the elastic effects are a cautionary tale for defect calculations in ionic materials, particularly when employing computationally expensive methods or when modelling large defect clusters. We propose two computationally practicable methods to test the magnitude of the elastic self-interaction in any ionic system.