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An empirical, yet practical way to predict the band gap in solids by using density functional band structure calculations

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Band structure calculations based on density functional theory (DFT) with local or gradient-corrected exchange-correlation potentials are known to severely underestimate the band gap of semiconducting and insulating materials. Alternative approaches have been proposed: from semiempirical setups, such as the so-called DFT +U, to hybrid density functionals using a fraction of nonlocal Fock exchange, to modifications of semilocal density functionals. However, the resulting methods appear to be material dependent and lack theoretical rigor. The rigorous many-body perturbation theory based on GW methods provides accurate results but at a very high computational cost. Hereby, we show that a linear correlation between the electronic band gaps obtained from standard DFT and GW approaches exists for most materials and argue that (1) this is a strong indication that the problem of predicting band gaps from standard DFT calculation arises from the assignment of a physical meaning to the Kohn-Sham energy levels rather than from intrinsic errors of the DFT methods and (2) it provides a practical way to obtain GW-like quality results from standard DFT calculations. The latter will be especially useful for systems where the unit cell involves a large number of atoms as in the case of doped or defect-containing materials for which GW calculations become unfeasible.

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MORALES GARCÍA, Ángel, VALERO MONTERO, Rosendo, ILLAS I RIERA, Francesc. An empirical, yet practical way to predict the band gap in solids by using density functional band structure calculations. _Journal of Physical Chemistry C_. 2017. Vol. 121, núm. 34, pàgs. 18862-18866. [consulta: 14 de gener de 2026]. ISSN: 1932-7447. [Disponible a: https://hdl.handle.net/2445/165598]

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