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The Journal of Chemical Physics
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Approaching the basis set limit in Gaussian-orbital-based periodic calculations with transferability: Performance of pure density functionals for simple semiconductors

Authors: Joonho Lee; Xintian Feng; Leonardo A. Cunha; Jérôme F. Gonthier; Evgeny Epifanovsky; Martin Head-Gordon;

Approaching the basis set limit in Gaussian-orbital-based periodic calculations with transferability: Performance of pure density functionals for simple semiconductors

Abstract

Simulating solids with quantum chemistry methods and Gaussian-type orbitals (GTOs) has been gaining popularity. Nonetheless, there are few systematic studies that assess the basis set incompleteness error (BSIE) in these GTO-based simulations over a variety of solids. In this work, we report a GTO-based implementation for solids and apply it to address the basis set convergence issue. We employ a simple strategy to generate large uncontracted (unc) GTO basis sets that we call the unc-def2-GTH sets. These basis sets exhibit systematic improvement toward the basis set limit as well as good transferability based on application to a total of 43 simple semiconductors. Most notably, we found the BSIE of unc-def2-QZVP-GTH to be smaller than 0.7 mEh per atom in total energies and 20 meV in bandgaps for all systems considered here. Using unc-def2-QZVP-GTH, we report bandgap benchmarks of a combinatorially designed meta-generalized gradient approximation (mGGA) functional, B97M-rV, and show that B97M-rV performs similarly (a root-mean-square-deviation of 1.18 eV) to other modern mGGA functionals, M06-L (1.26 eV), MN15-L (1.29 eV), and Strongly Constrained and Appropriately Normed (SCAN) (1.20 eV). This represents a clear improvement over older pure functionals such as local density approximation (1.71 eV) and Perdew-Burke-Ernzerhof (PBE) (1.49 eV), although all these mGGAs are still far from being quantitatively accurate. We also provide several cautionary notes on the use of our uncontracted bases and on future research on GTO basis set development for solids.

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United States
Keywords

Chemical Physics (physics.chem-ph), Condensed Matter - Materials Science, Engineering, Chemical Physics, Physics - Chemical Physics, Physical Sciences, Chemical Sciences, Materials Science (cond-mat.mtrl-sci), FOS: Physical sciences, Computational Physics (physics.comp-ph), Physics - Computational Physics

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selected citations
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This is an alternative to the "Influence" indicator, which also reflects the overall/total impact of an article in the research community at large, based on the underlying citation network (diachronically).
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popularity
This indicator reflects the "current" impact/attention (the "hype") of an article in the research community at large, based on the underlying citation network.
BIP!Popularity provided by BIP!
influence
This indicator reflects the overall/total impact of an article in the research community at large, based on the underlying citation network (diachronically).
BIP!Influence provided by BIP!
impulse
This indicator reflects the initial momentum of an article directly after its publication, based on the underlying citation network.
BIP!Impulse provided by BIP!
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