Localizing holes as polarons and predicting band gaps, defect levels, and delithiation energies of solid-state materials with a local exchange-correlation functional

Shuping Huang, Pragya Verma, Donald G Truhlar

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15 Scopus citations


This work assesses 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.

Original languageEnglish (US)
JournalJournal of Physical Chemistry C
Issue number39
StatePublished - 2017

Bibliographical note

Funding Information:
The authors are grateful to Peter Deaḱ for suggestions on the doped silicon calculations. S.H. acknowledges financial support from the National Natural Science Foundation of China (No. 21703036). As part of Nanoporous Materials Genome Center, this work was partially supported by the U.S. Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences, under Award DE-FG02-12ER16362. Computations were performed using resources of (1) the Molecular Science Computing Facility in the William R. Wiley Environmental Molecular Sciences Laboratory of Pacific Northwest National Laboratory sponsored by the U.S. Department of Energy, (2) Minnesota Supercomputing Institute, and (3) the National Energy Research Scientific Computing Center.

Publisher Copyright:
© 2017 American Chemical Society.


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