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Title: Accuracy of ab initio electron correlation and electron densities in vanadium dioxide

Here, diffusion quantum Monte Carlo results are used as a reference to analyze properties related to phase stability and magnetism in vanadium dioxide computed with various formulations of density functional theory. We introduce metrics related to energetics, electron densities and spin densities that give us insight on both local and global variations in the antiferromagnetic M1 and R phases. Importantly, these metrics can address contributions arising from the challenging description of the 3d orbital physics in this material. We observe that the best description of energetics between the structural phases does not correspond to the best accuracy in the charge density, which is consistent with observations made recently by Medvedev et~al. in the context of isolated atoms. However, we do find evidence that an accurate spin density connects to correct energetic ordering of different magnetic states in VO$$_2$$, although local, semilocal, and meta-GGA functionals tend to erroneously favor demagnetization of the vanadium sites. The recently developed SCAN functional stands out as remaining nearly balanced in terms of magnetization across the M1-R transition and correctly predicting the ground state crystal structure. In addition to ranking current density functionals, our reference energies and densities serve as important benchmarks for future functional development.
Authors:
ORCiD logo [1] ; ORCiD logo [1] ; ORCiD logo [1] ;  [2] ; ORCiD logo [1] ; ORCiD logo [1]
  1. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  2. Argonne National Lab. (ANL), Lemont, IL (United States); Northwestern Univ., Evanston, IL (United States)
Publication Date:
Grant/Contract Number:
AC05-00OR22725; AC02-05CH11231; AC02-06CH11357
Type:
Accepted Manuscript
Journal Name:
Physical Review Materials
Additional Journal Information:
Journal Volume: 1; Journal Issue: 6; Journal ID: ISSN 2475-9953
Publisher:
American Physical Society (APS)
Research Org:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE
OSTI Identifier:
1410929
Alternate Identifier(s):
OSTI ID: 1410385; OSTI ID: 1413747

Kylänpää, Ilkka, Balachandran, Janakiraman, Ganesh, Panchapakesan, Heinonen, Olle, Kent, Paul R. C., and Krogel, Jaron T.. Accuracy of ab initio electron correlation and electron densities in vanadium dioxide. United States: N. p., Web. doi:10.1103/PhysRevMaterials.1.065408.
Kylänpää, Ilkka, Balachandran, Janakiraman, Ganesh, Panchapakesan, Heinonen, Olle, Kent, Paul R. C., & Krogel, Jaron T.. Accuracy of ab initio electron correlation and electron densities in vanadium dioxide. United States. doi:10.1103/PhysRevMaterials.1.065408.
Kylänpää, Ilkka, Balachandran, Janakiraman, Ganesh, Panchapakesan, Heinonen, Olle, Kent, Paul R. C., and Krogel, Jaron T.. 2017. "Accuracy of ab initio electron correlation and electron densities in vanadium dioxide". United States. doi:10.1103/PhysRevMaterials.1.065408.
@article{osti_1410929,
title = {Accuracy of ab initio electron correlation and electron densities in vanadium dioxide},
author = {Kylänpää, Ilkka and Balachandran, Janakiraman and Ganesh, Panchapakesan and Heinonen, Olle and Kent, Paul R. C. and Krogel, Jaron T.},
abstractNote = {Here, diffusion quantum Monte Carlo results are used as a reference to analyze properties related to phase stability and magnetism in vanadium dioxide computed with various formulations of density functional theory. We introduce metrics related to energetics, electron densities and spin densities that give us insight on both local and global variations in the antiferromagnetic M1 and R phases. Importantly, these metrics can address contributions arising from the challenging description of the 3d orbital physics in this material. We observe that the best description of energetics between the structural phases does not correspond to the best accuracy in the charge density, which is consistent with observations made recently by Medvedev et~al. in the context of isolated atoms. However, we do find evidence that an accurate spin density connects to correct energetic ordering of different magnetic states in VO$_2$, although local, semilocal, and meta-GGA functionals tend to erroneously favor demagnetization of the vanadium sites. The recently developed SCAN functional stands out as remaining nearly balanced in terms of magnetization across the M1-R transition and correctly predicting the ground state crystal structure. In addition to ranking current density functionals, our reference energies and densities serve as important benchmarks for future functional development.},
doi = {10.1103/PhysRevMaterials.1.065408},
journal = {Physical Review Materials},
number = 6,
volume = 1,
place = {United States},
year = {2017},
month = {11}
}

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