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Title: Excitation spectra of aromatic molecules within a real-space GW-BSE formalism: Role of self-consistency and vertex corrections

Here, we present first-principles calculations on the vertical ionization potentials (IPs), electron affinities (EAs), and singlet excitation energies on an aromatic-molecule test set (benzene, thiophene, 1,2,5-thiadiazole, naphthalene, benzothiazole, and tetrathiafulvalene) within the GW and Bethe-Salpeter equation (BSE) formalisms. Our computational framework, which employs a real-space basis for ground-state and a transition-space basis for excited-state calculations, is well suited for high-accuracy calculations on molecules, as we show by comparing against G0W0 calculations within a plane-wave-basis formalism. We then generalize our framework to test variants of the GW approximation that include a local density approximation (LDA)–derived vertex function (ΓLDA ) and quasiparticle-self-consistent (QS) iterations. We find that ΓLDA and quasiparticle self-consistency shift IPs and EAs by roughly the same magnitude, but with opposite sign for IPs and the same sign for EAs. G0W0 and QS GWΓLDA are more accurate for IPs, while G0W0ΓLDA and QSGW are best for EAs. For optical excitations, we find that perturbative GW-BSE underestimates the singlet excitation energy, while self-consistent GW-BSE results in good agreement with previous best-estimate values for both valence and Rydberg excitations. Finally, our work suggests that a hybrid approach, in which G0W0 energies are used for occupied orbitals and G0W0ΓLDA for unoccupied orbitals, alsomore » yields optical excitation energies in good agreement with experiment but at a smaller computational cost.« less
ORCiD logo [1] ;  [2] ;  [3] ;  [3] ;  [2] ;  [4]
  1. Univ. of Illinois at Chicago, Chicago, IL (United States); National Institute of Standards and Technology, Gaithersburg, MD (United States)
  2. Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  3. Univ. of Texas at Austin, Austin, TX (United States)
  4. Univ. of Illinois at Chicago, Chicago, IL (United States)
Publication Date:
Grant/Contract Number:
SC0001853; FG02-09ER16072; AC02-05CH11231; SC0008877
Accepted Manuscript
Journal Name:
Physical Review B
Additional Journal Information:
Journal Volume: 94; Journal Issue: 8; Journal ID: ISSN 2469-9950
American Physical Society (APS)
Research Org:
Univ. of Illinois at Chicago, Chicago, IL (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
OSTI Identifier:
Alternate Identifier(s):
OSTI ID: 1294714