Recommendation of Orbitals for G0W0Calculations on Molecules and Crystals

Linyao Zhang, Yinan Shu, Chang Xing, Xiye Chen, Shaozeng Sun, Yudong Huang, Donald G. Truhlar

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The many-body GW approximation, especially the G0W0 method, has been widely used for condensed matter and molecules to calculate quasiparticle energies for ionization, electron attachment, and band gaps. Because G0W0 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 G0W0 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).

Original languageEnglish (US)
Pages (from-to)3523-3537
Number of pages15
JournalJournal of Chemical Theory and Computation
Issue number6
StatePublished - Jun 14 2022

Bibliographical note

Funding Information:
This work was supported in part by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under award DE-SC0015997 and by the Heilongjiang Postdoctoral Program (grant no. LBH-Z21136).

Publisher Copyright:
© 2022 American Chemical Society.

PubMed: MeSH publication types

  • Journal Article


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