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Title: Localizing Holes as Polarons and Predicting Band Gaps, Defect Levels, and Delithiation Energies of Solid-State Materials with a Local Exchange-Correlation Functional

Abstract

Here, we assess the performance of seven exchange–correlation functionals (some with and some without a Hubbard U correction) for their ability (i) to predict band gaps of silicon, diamond, and Li-ion battery cathode materials, (ii) to localize hole polarons and predict delithiation energies in Li-ion battery cathode materials, and (iii) to predict transition levels of charge carriers of doped silicon and diamond. Both local and hybrid exchange–correlation functionals were tested. The local functionals tend to underestimate band gaps and delocalize polarons. The hybrid functionals very often give a good description of both properties, but they may not be practical for calculations involving large unit cells, large ensembles, or dynamics, and therefore a local functional with a Hubbard U correction is often used (giving the method called DFT+U), where the value of a parameter U is adjusted according to the system and the property being investigated. Keeping in mind the importance of computational cost and the undesirability of having to adjust an empirical parameter for each system or property of interest, we recently developed a local functional, namely HLE17, to try to accurately predict band gaps and excitation energies, and we validated it using mostly main-group solids and molecules. Here wemore » test the performance of HLE17 for its ability to predict band gaps and localize polarons in other solid-state materials, and we compare its performance to that of popular local functionals (PBE, PBEsol, and TPSS), a range-separated hybrid functional with screened exchange (HSE06), and DFT+U. We find that HLE17 predicts more accurate band gaps than other local functionals and can localize holes as polarons, which other local functionals usually fail to do, and for a number of cases it is comparable in performance quality to Hubbard-corrected functionals without the need for system-specific parametrization and to hybrid functionals without the high cost. Because HLE17 does not predict accurate lattice constants, we use the single-point method of quantum chemistry, where the geometry is optimized with one functional and the band gap is calculated with HLE17, or we perform calculations with the lattice constants obtained by TPSS and both the fractional intracell coordinates and the electronic structure obtained by HLE17 (a new method denoted HLE17\\TPSS). In particular, we performed calculations by HLE17//TPSS, HLE17//HSE06, HLE17//DFT+U, and HLE17\\TPSS, and these methods usually agree well with each other and give values similar to experiment.« less

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [2]
  1. Fuzhou Univ., Fujian (China). College of Chemistry; Univ. of Minnesota, Minneapolis, MN (United States). Dept. of Chemistry, Chemical Theory Center, and Minnesota Supercomputing Inst.
  2. Univ. of Minnesota, Minneapolis, MN (United States). Dept. of Chemistry, Chemical Theory Center, Minnesota Supercomputing Inst., and Nanoporous Materials Genome Center
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1483386
Grant/Contract Number:  
FG02-12ER16362; SC0008688
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 121; Journal Issue: 43; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Huang, Shuping, Verma, Pragya, and Truhlar, Donald G. Localizing Holes as Polarons and Predicting Band Gaps, Defect Levels, and Delithiation Energies of Solid-State Materials with a Local Exchange-Correlation Functional. United States: N. p., 2017. Web. doi:10.1021/acs.jpcc.7b09000.
Huang, Shuping, Verma, Pragya, & Truhlar, Donald G. Localizing Holes as Polarons and Predicting Band Gaps, Defect Levels, and Delithiation Energies of Solid-State Materials with a Local Exchange-Correlation Functional. United States. https://doi.org/10.1021/acs.jpcc.7b09000
Huang, Shuping, Verma, Pragya, and Truhlar, Donald G. Fri . "Localizing Holes as Polarons and Predicting Band Gaps, Defect Levels, and Delithiation Energies of Solid-State Materials with a Local Exchange-Correlation Functional". United States. https://doi.org/10.1021/acs.jpcc.7b09000. https://www.osti.gov/servlets/purl/1483386.
@article{osti_1483386,
title = {Localizing Holes as Polarons and Predicting Band Gaps, Defect Levels, and Delithiation Energies of Solid-State Materials with a Local Exchange-Correlation Functional},
author = {Huang, Shuping and Verma, Pragya and Truhlar, Donald G.},
abstractNote = {Here, we assess the performance of seven exchange–correlation functionals (some with and some without a Hubbard U correction) for their ability (i) to predict band gaps of silicon, diamond, and Li-ion battery cathode materials, (ii) to localize hole polarons and predict delithiation energies in Li-ion battery cathode materials, and (iii) to predict transition levels of charge carriers of doped silicon and diamond. Both local and hybrid exchange–correlation functionals were tested. The local functionals tend to underestimate band gaps and delocalize polarons. The hybrid functionals very often give a good description of both properties, but they may not be practical for calculations involving large unit cells, large ensembles, or dynamics, and therefore a local functional with a Hubbard U correction is often used (giving the method called DFT+U), where the value of a parameter U is adjusted according to the system and the property being investigated. Keeping in mind the importance of computational cost and the undesirability of having to adjust an empirical parameter for each system or property of interest, we recently developed a local functional, namely HLE17, to try to accurately predict band gaps and excitation energies, and we validated it using mostly main-group solids and molecules. Here we test the performance of HLE17 for its ability to predict band gaps and localize polarons in other solid-state materials, and we compare its performance to that of popular local functionals (PBE, PBEsol, and TPSS), a range-separated hybrid functional with screened exchange (HSE06), and DFT+U. We find that HLE17 predicts more accurate band gaps than other local functionals and can localize holes as polarons, which other local functionals usually fail to do, and for a number of cases it is comparable in performance quality to Hubbard-corrected functionals without the need for system-specific parametrization and to hybrid functionals without the high cost. Because HLE17 does not predict accurate lattice constants, we use the single-point method of quantum chemistry, where the geometry is optimized with one functional and the band gap is calculated with HLE17, or we perform calculations with the lattice constants obtained by TPSS and both the fractional intracell coordinates and the electronic structure obtained by HLE17 (a new method denoted HLE17\\TPSS). In particular, we performed calculations by HLE17//TPSS, HLE17//HSE06, HLE17//DFT+U, and HLE17\\TPSS, and these methods usually agree well with each other and give values similar to experiment.},
doi = {10.1021/acs.jpcc.7b09000},
journal = {Journal of Physical Chemistry. C},
number = 43,
volume = 121,
place = {United States},
year = {2017},
month = {10}
}

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Figures / Tables:

Figure 1 Figure 1: (a) Supercell of Li8ZrO6. The zirconium ions occupy octahedral sites, and the lithium ions occupy both tetrahedral sites (labeled as Td) and octahedral sites (labeled as Oh). (b) Supercell of LiFePO4.

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How well can density functional theory and pair-density functional theory predict the correct atomic charges for dissociation and accurate dissociation energetics of ionic bonds?
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