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This content will become publicly available on September 15, 2018

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

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 effect are also important in the description of defects in ionic compounds and can lead to qualitatively incorrect conclusions if inadequatly 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 themore » 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 (e.g. hybrid functionals) 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. In commonly studies oxides, where electrostatic effects would be expected to be dominant, it is the elastic effects that dictate the need for larger supercells | greater than 96 atoms.« less
 [1] ;  [2]
  1. Univ. of New South Wales, Sydney, NSW (Australia)
  2. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Publication Date:
Report Number(s):
Journal ID: ISSN 2469-9950; PRBMDO; TRN: US1702843
Grant/Contract Number:
AC52-06NA25396; AC52- 06NA25396
Accepted Manuscript
Journal Name:
Physical Review B
Additional Journal Information:
Journal Volume: 96; Journal Issue: 9; Journal ID: ISSN 2469-9950
American Physical Society (APS)
Research Org:
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Sponsoring Org:
USDOE Office of Nuclear Energy (NE); USDOE National Nuclear Security Administration (NNSA)
Country of Publication:
United States
OSTI Identifier:
Alternate Identifier(s):
OSTI ID: 1390645