Accuracy of Hybrid Functionals with Non-Self-Consistent Kohn-Sham Orbitals for Predicting the Properties of Semiconductors

• Published in: Journal of chemical theory and computation 2020-06, Vol.16 (6), p.3543-3557
• Main Authors: Skelton, Jonathan M, Gunn, David S D, Metz, Sebastian, Parker, Stephen C
• Format: Article
• Language: English
• Subjects: Accuracy; Bulk modulus; Computational efficiency; Computing costs; Computing time; Conduction bands; Density functional theory; Dielectric properties; Electronic structure; Energy gap; Orbitals; Physical properties; Semiconductors; Transition metal oxides
• ISSN: 1549-9618; 1549-9626
• DOI: 10.1021/acs.jctc.9b01218

Accurately modeling the electronic structure of materials is a persistent challenge to high-throughput screening. A promising means of balancing accuracy against computational cost is non-self-consistent calculations with hybrid density-functional theory, where the electronic band energies are evaluated using a hybrid functional from orbitals obtained with a less demanding (semi)local functional. We have quantified the performance of this technique for predicting the physical properties of 16 tetrahedral semiconductors with bandgaps from 0.2 to 5.5 eV. Provided the base functional predicts a nonmetallic electronic structure, bandgaps within 5% of the PBE0 and HSE06 gaps can be obtained with an order of magnitude reduction in computing time. The positions of the valence and conduction band extrema and the Fermi level are well reproduced, enabling calculation of the band dispersion, density of states, and dielectric properties using Fermi's Golden Rule. While the error in the non-self-consistent total energies is ∼50 meV atom , the energy-volume curves are reproduced accurately enough to obtain the equilibrium volume and bulk modulus with minimal error. We also test the dielectric-dependent scPBE0 functional and obtain bandgaps and dielectric constants to within 2.5% of the self-consistent results, which amounts to a significant improvement over self-consistent PBE0 for a similar computational cost. We identify cases where the non-self-consistent approach is expected to perform poorly and demonstrate that partial self-consistency provides a practical and efficient workaround. Finally, we perform proof-of-concept calculations on CoO and NiO to demonstrate the applicability of the technique to strongly correlated open-shell transition-metal oxides.