Hybrid-functional calculations with plane-wave basis sets: Effect of singularity correction on total energies, energy eigenvalues, and defect energy levels

Abstract

When described through a plane-wave basis set, the inclusion of exact nonlocal exchange in hybrid functionals gives rise to a singularity, which slows down the convergence with the density of sampled $k$ points in reciprocal space. In this work, we investigate to what extent the treatment of the singularity through the use of an auxiliary function is effective for $k$-point samplings of limited density, in comparison to analogous calculations performed with semilocal density functionals. Our analysis applies, for instance, to calculations in which the Brillouin zone is sampled at the sole $\ensuremath{\Gamma}$ point, as often occurs in the study of surfaces, interfaces, and defects or in molecular-dynamics simulations. In the adopted formulation, the treatment of the singularity results in the addition of a correction term to the total energy. The energy eigenvalue spectrum is affected by a downwards shift in the energy eigenvalues of the occupied states, while those of the unoccupied states remain unaffected. Analogous corrections also speed up the convergence of screened exchange interactions despite the absence of a proper singularity. Focusing first on neutral systems, both finite and extended, we show that the account of the singularity corrections bears convergence properties which are quantitatively similar to those observed with semilocal density functionals. We emphasize that this is not the case for uncorrected energies, particularly for elongated simulation cells for which qualitatively different trends are found. We then consider differences between total energies of systems differing by their charge state. For systems involving localized electron states, such as ionization potentials and electron affinities of molecular systems or charge transition levels of point defects, the proper account of the singularity correction yields convergence properties which are similar to those of neutral systems. In the case of extended systems, such energy differences provide an alternative way to determine the band edges, but are found to converge more slowly with simulation cells than in corresponding semilocal functionals because of the exchange self-interaction associated to the extra charge.