Importance of elastic finite-size effects: Neutral defects in ionic compounds
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 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 »
- Authors:
-
- Univ. of New South Wales, Sydney, NSW (Australia)
- Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
- Publication Date:
- Research Org.:
- Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)
- Sponsoring Org.:
- USDOE Office of Nuclear Energy (NE); USDOE National Nuclear Security Administration (NNSA)
- OSTI Identifier:
- 1396125
- Alternate Identifier(s):
- OSTI ID: 1390645
- Report Number(s):
- LA-UR-17-22161
Journal ID: ISSN 2469-9950; PRBMDO; TRN: US1702843
- Grant/Contract Number:
- AC52-06NA25396; AC52- 06NA25396
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Physical Review B
- Additional Journal Information:
- Journal Volume: 96; Journal Issue: 9; Journal ID: ISSN 2469-9950
- Publisher:
- American Physical Society (APS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY
Citation Formats
Burr, P. A., and Cooper, M. W. D. Importance of elastic finite-size effects: Neutral defects in ionic compounds. United States: N. p., 2017.
Web. doi:10.1103/PhysRevB.96.094107.
Burr, P. A., & Cooper, M. W. D. Importance of elastic finite-size effects: Neutral defects in ionic compounds. United States. https://doi.org/10.1103/PhysRevB.96.094107
Burr, P. A., and Cooper, M. W. D. Fri .
"Importance of elastic finite-size effects: Neutral defects in ionic compounds". United States. https://doi.org/10.1103/PhysRevB.96.094107. https://www.osti.gov/servlets/purl/1396125.
@article{osti_1396125,
title = {Importance of elastic finite-size effects: Neutral defects in ionic compounds},
author = {Burr, P. A. and Cooper, M. W. D.},
abstractNote = {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 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 (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.},
doi = {10.1103/PhysRevB.96.094107},
journal = {Physical Review B},
number = 9,
volume = 96,
place = {United States},
year = {Fri Sep 15 00:00:00 EDT 2017},
month = {Fri Sep 15 00:00:00 EDT 2017}
}
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