The Conundrum of Relaxation Volumes in First-Principles Calculations of Charged Defects in UO2
Abstract
The defect relaxation volumes obtained from density-functional theory (DFT) calculations of charged vacancies and interstitials are much larger than their neutral counterparts, seemingly unphysically large. We focus on UO2 as our primary material of interest, but also consider Si and GaAs to reveal the generality of our results. In this work, we investigate the possible reasons for this and revisit the methods that address the calculation of charged defects in periodic DFT. We probe the dependence of the proposed energy corrections to charged defect formation energies on relaxation volumes and find that corrections such as potential alignment remain ambiguous with regards to its contribution to the charged defect relaxation volume. We also investigate the volume for the net neutral defect reactions comprising individual charged defects, and find that the aggregate formation volumes have reasonable magnitudes. This work highlights the issue that, as is well-known for defect formation energies, the defect formation volumes depend on the choice of reservoir. We show that considering the change in volume of the electron reservoir in the formation reaction of the charged defects, analogous to how volumes of atoms are accounted for in defect formation volumes, can renormalize the formation volumes of charged defects suchmore »
- Authors:
- 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:
- 1577208
- Alternate Identifier(s):
- OSTI ID: 1597330
- Report Number(s):
- LA-UR-17-22816
Journal ID: ISSN 2076-3417; ASPCC7; PII: app9245276
- Grant/Contract Number:
- 10-2258; Nuclear Energy Advanced Modeling and Simulations; 89233218CNA000001
- Resource Type:
- Published Article
- Journal Name:
- Applied Sciences
- Additional Journal Information:
- Journal Name: Applied Sciences Journal Volume: 9 Journal Issue: 24; Journal ID: ISSN 2076-3417
- Publisher:
- MDPI
- Country of Publication:
- Switzerland
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE; defects; elasticity; relaxation volume; dipole tensor; urania; density functional theory
Citation Formats
Goyal, Anuj, Mathew, Kiran, Hennig, Richard G., Chernatynskiy, Aleksandr, Stanek, Christopher R., Murphy, Samuel T., Andersson, David A., Phillpot, Simon R., and Uberuaga, Blas P. The Conundrum of Relaxation Volumes in First-Principles Calculations of Charged Defects in UO2. Switzerland: N. p., 2019.
Web. doi:10.3390/app9245276.
Goyal, Anuj, Mathew, Kiran, Hennig, Richard G., Chernatynskiy, Aleksandr, Stanek, Christopher R., Murphy, Samuel T., Andersson, David A., Phillpot, Simon R., & Uberuaga, Blas P. The Conundrum of Relaxation Volumes in First-Principles Calculations of Charged Defects in UO2. Switzerland. https://doi.org/10.3390/app9245276
Goyal, Anuj, Mathew, Kiran, Hennig, Richard G., Chernatynskiy, Aleksandr, Stanek, Christopher R., Murphy, Samuel T., Andersson, David A., Phillpot, Simon R., and Uberuaga, Blas P. Wed .
"The Conundrum of Relaxation Volumes in First-Principles Calculations of Charged Defects in UO2". Switzerland. https://doi.org/10.3390/app9245276.
@article{osti_1577208,
title = {The Conundrum of Relaxation Volumes in First-Principles Calculations of Charged Defects in UO2},
author = {Goyal, Anuj and Mathew, Kiran and Hennig, Richard G. and Chernatynskiy, Aleksandr and Stanek, Christopher R. and Murphy, Samuel T. and Andersson, David A. and Phillpot, Simon R. and Uberuaga, Blas P.},
abstractNote = {The defect relaxation volumes obtained from density-functional theory (DFT) calculations of charged vacancies and interstitials are much larger than their neutral counterparts, seemingly unphysically large. We focus on UO2 as our primary material of interest, but also consider Si and GaAs to reveal the generality of our results. In this work, we investigate the possible reasons for this and revisit the methods that address the calculation of charged defects in periodic DFT. We probe the dependence of the proposed energy corrections to charged defect formation energies on relaxation volumes and find that corrections such as potential alignment remain ambiguous with regards to its contribution to the charged defect relaxation volume. We also investigate the volume for the net neutral defect reactions comprising individual charged defects, and find that the aggregate formation volumes have reasonable magnitudes. This work highlights the issue that, as is well-known for defect formation energies, the defect formation volumes depend on the choice of reservoir. We show that considering the change in volume of the electron reservoir in the formation reaction of the charged defects, analogous to how volumes of atoms are accounted for in defect formation volumes, can renormalize the formation volumes of charged defects such that they are comparable to neutral defects. This approach enables the description of the elastic properties of isolated charged defects within an overall neutral material.},
doi = {10.3390/app9245276},
journal = {Applied Sciences},
number = 24,
volume = 9,
place = {Switzerland},
year = {Wed Dec 04 00:00:00 EST 2019},
month = {Wed Dec 04 00:00:00 EST 2019}
}
https://doi.org/10.3390/app9245276
Web of Science
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