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Title: The conundrum of relaxation volumes in first-principles calculations of charged defects

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 » 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.« less

Authors:
 [1];  [1];  [1];  [2]; ORCiD logo [3];  [4]; ORCiD logo [3];  [1]; ORCiD logo [3]
  1. University of Florida
  2. Missouri University of Science and Technology
  3. Los Alamos National Laboratory
  4. Lancaster University
Publication Date:
Research Org.:
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Sponsoring Org.:
USDOE Office of Nuclear Energy (NE)
OSTI Identifier:
1577208
Alternate Identifier(s):
OSTI ID: 1597330
Report Number(s):
LA-UR-17-22816
Journal ID: 2076-3417 (Electronic)
Grant/Contract Number:  
89233218CNA000001; 10-2258; Nuclear Energy Advanced Modeling and Simulations
Resource Type:
Published Article
Journal Name:
Applied Sciences
Additional Journal Information:
Journal Volume: 9; Journal Issue: 24
Country of Publication:
United States
Language:
English

Citation Formats

Goyal, Anuj, Mathew, Kiran, Hennig, Richard G., Chernatynskiy, Aleksandr, Stanek, Christopher Richard, Murphy, Samuel T., Andersson, Anders David Ragnar, Phillpot, Simon R., and Uberuaga, Blas P. The conundrum of relaxation volumes in first-principles calculations of charged defects. United States: N. p., 2019. Web. doi:10.3390/app9245276.
Goyal, Anuj, Mathew, Kiran, Hennig, Richard G., Chernatynskiy, Aleksandr, Stanek, Christopher Richard, Murphy, Samuel T., Andersson, Anders David Ragnar, Phillpot, Simon R., & Uberuaga, Blas P. The conundrum of relaxation volumes in first-principles calculations of charged defects. United States. doi:10.3390/app9245276.
Goyal, Anuj, Mathew, Kiran, Hennig, Richard G., Chernatynskiy, Aleksandr, Stanek, Christopher Richard, Murphy, Samuel T., Andersson, Anders David Ragnar, Phillpot, Simon R., and Uberuaga, Blas P. Mon . "The conundrum of relaxation volumes in first-principles calculations of charged defects". United States. doi:10.3390/app9245276.
@article{osti_1577208,
title = {The conundrum of relaxation volumes in first-principles calculations of charged defects},
author = {Goyal, Anuj and Mathew, Kiran and Hennig, Richard G. and Chernatynskiy, Aleksandr and Stanek, Christopher Richard and Murphy, Samuel T. and Andersson, Anders David Ragnar 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 = {United States},
year = {2019},
month = {12}
}

Journal Article:
Free Publicly Available Full Text
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DOI: 10.3390/app9245276

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