Recommendation of Orbitals for G0W0 Calculations on Molecules and Crystals

The many-body GW approximation, especially the G(0)W(0) method, has been widely used for condensed matter and molecules to calculate quasiparticle energies for ionization, electron attachment, and band gaps. Because G(0)W(0) calculations are well-known to have a strong dependence on the orbitals, the goal of the present work is to provide guidance on the choice of density functional used to generate orbitals and to recommend a choice that gives the most broadly accurate results. We have systematically investigated the dependence of G(0)W(0) calculations on the orbitals for 100 molecules and 8 crystals by considering orbitals obtained with a diverse set of Kohn-Sham (KS) and generalized KS (GKS) functionals (63 functionals plus Hartree-Fock). The percentage of Hartree-Fock exchange employed in density functionals has been found to have strong influence on the predicted molecular ionization energy and crystal fundamental band gaps (with optimum values between 40 and 56%), but to have less effect on predicting molecular electron affinities. The low cost of the Gaussian implementation, even with hybrid functionals in periodic calculations, the better performance of global hybrids as compared to range-separated hybrids of either than screened exchange or long-range-corrected type, and the relatively low cost of global-hybrid-functional periodic calculations using Gaussians means that one can employ global-hybrid functionals at a very reasonable cost and obtain more accurate band gaps of semiconductors than are obtained by the methods currently widely employed, namely local gradient approximations. We single out three global-hybrid functionals that give especially good results for both molecules (100 in the test set) and crystals (8 in the test set, for all of which our benchmark data are the proper band gap rather than an optical band gap uncorrected for exciton effects).

Automated summary

The present study systematically investigates the dependence of G(0)W(0) calculations on the choice of orbitals, finding that the percentage of Hartree-Fock exchange in density functionals strongly influences the predicted molecular ionization energy and crystal band gaps. The study also suggests that global-hybrid functionals provide more accurate band gaps for semiconductors at a reasonable cost compared to widely employed methods.