title: Accurate Ionization Potentials and Electron Affinities of Acceptor Molecules III: A Benchmark of GW Methods.
abstract: The performance of different GW methods is assessed for a set of 24 organic acceptors. Errors are evaluated with respect to coupled cluster singles, doubles, and perturbative triples [CCSD(T)] reference data for the vertical ionization potentials (IPs) and electron affinities (EAs), extrapolated to the complete basis set limit. Additional comparisons are made to experimental data, where available. We consider fully self-consistent GW (scGW), partial self-consistency in the Green's function (scGW0), non-self-consistent G0W0 based on several mean-field starting points, and a "beyond GW" second-order screened exchange (SOSEX) correction to G0W0. We also describe the implementation of the self-consistent Coulomb hole with screened exchange method (COHSEX), which serves as one of the mean-field starting points. The best performers overall are G0W0+SOSEX and G0W0 based on an IP-tuned long-range corrected hybrid functional with the former being more accurate for EAs and the latter for IPs. Both provide a balanced treatment of localized vs delocalized states and valence spectra in good agreement with photoemission spectroscopy (PES) experiments.
authors.affiliation: Physics and Engineering Physics, Tulane University , New Orleans, Louisiana 70118, United States.
authors.forename: Joseph W
authors.initials: JW
authors.lastname: Knight
authors.affiliation: Physics and Engineering Physics, Tulane University , New Orleans, Louisiana 70118, United States.
authors.forename: Xiaopeng
authors.initials: X
authors.lastname: Wang
authors.affiliation: Computational Chemistry, University of Potsdam , 14476 Potsdam, Germany.
authors.forename: Lukas
authors.initials: L
authors.lastname: Gallandi
authors.affiliation: Department of Chemistry and Biochemistry, Auburn University , Auburn, Alabama 36849-5312, United States.
authors.forename: Olga
authors.initials: O
authors.lastname: Dolgounitcheva
authors.affiliation: Key Laboratory of Quantum Information, University of Science and Technology of China , Hefei, Anhui 230026, China.
authors.forename: Xinguo
authors.initials: X
authors.lastname: Ren
authors.affiliation: Department of Chemistry and Biochemistry, Auburn University , Auburn, Alabama 36849-5312, United States.
authors.forename: J Vincent
authors.initials: JV
authors.lastname: Ortiz
authors.affiliation: COMP/Department of Applied Physics, Aalto University School of Science , P.O. Box 11100, FI-00076 Aalto, Finland.
authors.forename: Patrick
authors.initials: P
authors.lastname: Rinke
authors.affiliation: Computational Chemistry, University of Potsdam , 14476 Potsdam, Germany.
authors.forename: Thomas
authors.initials: T
authors.lastname: Körzdörfer
authors.affiliation: Physics and Engineering Physics, Tulane University , New Orleans, Louisiana 70118, United States.
authors.forename: Noa
authors.initials: N
authors.lastname: Marom