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Does DFT+U mimic hybrid density functionals?

  • Pragya Verma
  • Donald G. TruhlarEmail author
Regular Article

Abstract

This work examines the question of how a Hubbard U correction to a local exchange–correlation functional compares with adding Hartree–Fock exchange to a local functional for both solid-state and molecular properties. We compute a solid-state property, namely the band gap, and thermochemical molecular properties, in particular, main-group bond energies, transition metal–ligand bond energies, and barrier heights, to elucidate whether the DFT+U method mimics hybrid DFT. We find that a calculation with a Hubbard U correction may or may not mimic a hybrid functional—depending on the atom, the subshell, and the property to which it is applied. For band gaps, we find that adding a Hubbard U correction to the valence d orbitals of transition metals increases the band gap, which thereby gets closer to the experimental value, while adding a Hubbard U correction to valence s or p orbitals of main-group elements need not always increase the band gap. For molecular thermochemistry, we find that adding a Hubbard U correction to a local density functional need not have the same effect as adding Hartree–Fock exchange to a local density functional. For example when compared to a DFT calculation with a local exchange-correlation functional, hybrid DFT increases the barrier height in all cases, but DFT+U does not always increase the barrier height. For the band gaps of transition metal monoxides, the Hubbard-corrected results lowered the mean errors significantly and were comparable to what could be achieved with a much more expensive hybrid functional, but for reaction barrier heights and bond energies of molecules, the Hubbard correction was found to lower the mean error by only approximately a kcal/mol. As part of the analysis, we also compare VASP and Gaussian 09 calculations for the same density functional.

Keywords

Atomization energy Band gap Barrier height Bond energy Density functional theory Hubbard U correction Molecular thermochemistry Solid-state physics 

Notes

Acknowledgments

The authors thank Kaining Duanmu, Shuping Huang, Georg Kresse, and Haoyu Yu for helpful discussions. This work was supported by the Nanoporous Materials Genome Center funded by the US Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences, under award DE-FG02-12ER16362.

Compliance with ethical standards

Conflict of interest

The authors declare no competing financial interest.

Supplementary material

214_2016_1927_MOESM1_ESM.pdf (347 kb)
Supplementary material 1 (PDF 348 kb)

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Copyright information

© Springer-Verlag Berlin Heidelberg 2016

Authors and Affiliations

  1. 1.Department of Chemistry, Chemical Theory Center, Nanoporous Materials Genome Center, and Minnesota Supercomputing InstituteUniversity of MinnesotaMinneapolisUSA

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