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Title: Wannier–Koopmans method calculations for transition metal oxide band gaps

Abstract

The widely used density functional theory (DFT) has a major drawback of underestimating the band gaps of materials. Wannier–Koopmans method (WKM) was recently developed for band gap calculations with accuracy on a par with more complicated methods. WKM has been tested for main group covalent semiconductors, alkali halides, 2D materials, and organic crystals. Here we apply the WKM to another interesting type of material system: the transition metal (TM) oxides. TM oxides can be classified as either with d0 or d10 closed shell occupancy or partially occupied open shell configuration, and the latter is known to be strongly correlated Mott insulators. We found that, while WKM provides adequate band gaps for the d0 and d10 TM oxides, it fails to provide correct band gaps for the group with partially occupied d states. This issue is also found in other mean-field approaches like the GW calculations. We believe that the problem comes from a strong interaction between the occupied and unoccupied d-state Wannier functions in a partially occupied d-state system. We also found that, for pseudopotential calculations including deep core levels, it is necessary to remove the electron densities of these deep core levels in the Hartree and exchange–correlation energy functionalmore » when calculating the WKM correction parameters for the d-state Wannier functions.« less

Authors:
 [1];  [1]; ORCiD logo [2]
  1. Peking Univ., Shenzhen (China)
  2. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1630624
Grant/Contract Number:  
AC02-05CH11231; JCYJ20160226105838578; JCYJ20151015162256516
Resource Type:
Accepted Manuscript
Journal Name:
npj Computational Materials
Additional Journal Information:
Journal Volume: 6; Journal Issue: 1; Journal ID: ISSN 2057-3960
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; computational methods; electronic structure

Citation Formats

Weng, Mouyi, Pan, Feng, and Wang, Lin-Wang. Wannier–Koopmans method calculations for transition metal oxide band gaps. United States: N. p., 2020. Web. doi:10.1038/s41524-020-0302-0.
Weng, Mouyi, Pan, Feng, & Wang, Lin-Wang. Wannier–Koopmans method calculations for transition metal oxide band gaps. United States. https://doi.org/10.1038/s41524-020-0302-0
Weng, Mouyi, Pan, Feng, and Wang, Lin-Wang. Fri . "Wannier–Koopmans method calculations for transition metal oxide band gaps". United States. https://doi.org/10.1038/s41524-020-0302-0. https://www.osti.gov/servlets/purl/1630624.
@article{osti_1630624,
title = {Wannier–Koopmans method calculations for transition metal oxide band gaps},
author = {Weng, Mouyi and Pan, Feng and Wang, Lin-Wang},
abstractNote = {The widely used density functional theory (DFT) has a major drawback of underestimating the band gaps of materials. Wannier–Koopmans method (WKM) was recently developed for band gap calculations with accuracy on a par with more complicated methods. WKM has been tested for main group covalent semiconductors, alkali halides, 2D materials, and organic crystals. Here we apply the WKM to another interesting type of material system: the transition metal (TM) oxides. TM oxides can be classified as either with d0 or d10 closed shell occupancy or partially occupied open shell configuration, and the latter is known to be strongly correlated Mott insulators. We found that, while WKM provides adequate band gaps for the d0 and d10 TM oxides, it fails to provide correct band gaps for the group with partially occupied d states. This issue is also found in other mean-field approaches like the GW calculations. We believe that the problem comes from a strong interaction between the occupied and unoccupied d-state Wannier functions in a partially occupied d-state system. We also found that, for pseudopotential calculations including deep core levels, it is necessary to remove the electron densities of these deep core levels in the Hartree and exchange–correlation energy functional when calculating the WKM correction parameters for the d-state Wannier functions.},
doi = {10.1038/s41524-020-0302-0},
journal = {npj Computational Materials},
number = 1,
volume = 6,
place = {United States},
year = {2020},
month = {4}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Figures / Tables:

Fig. 1 Fig. 1: Band Gap comparison between WKM/LDA calculations and experimental results. Comparing the experimental band gaps against band gap calculated by WKM in SG15 pseudopotential (labeled as SG15-WKM), SG15 pseudopotential with core-level fixation (labeled as SG15-WKM-fix1), FHI pseudopotential (labeled as FHI–WKM) and LDA with SG15 (labeled as SG15-LDA) and FHImore » (labeled as FHI–LDA) pseudopotential.« less

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Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.