A Benchmark of GW Methods for Azabenzenes: Is the GW Approximation Good Enough?

Abstract

Many-body perturbation theory in the GW approximation is a useful method for describing electronic properties associated with charged excitations. A hierarchy of GW methods exists, starting from non-self-consistent G0W0, through partial self-consistency in the eigenvalues (ev-scGW) and in the Green function (scGW0), to fully self-consistent GW (scGW). Here, we assess the performance of these methods for benzene, pyridine, and the diazines. The quasiparticle spectra are compared to photoemission spectroscopy (PES) experiments with respect to all measured particle removal energies and the ordering of the frontier orbitals. We find that the accuracy of the calculated spectra does not match the expectations based on their level of self-consistency. In particular, for certain starting points G0W0 and scGW0 provide spectra in better agreement with the PES than scGW.

References in corpus (17)

• Renormalization of Molecular Electronic Levels at Metal-Molecule Interfaces
• Quasiparticle band structure based on a generalized Kohn-Sham scheme
• First-principles GW calculations for fullerenes, porphyrins, phtalocyanine, and other molecules of interest for organic photovoltaic applications
• Metallic conduction at organic charge-transfer interfaces
• Conserving GW scheme for nonequilibrium quantum transport in molecular contacts
• Renormalization of Molecular Quasiparticle Levels at Metal-Molecule Interfaces: Trends Across Binding Regimes
• Band convergence and linearization error correction of all-electron GW calculations: The extreme case of zinc oxide
• Band gap and band parameters of InN and GaN from quasiparticle energy calculations based on exact-exchange density-functional theory
• Exact-exchange based quasiparticle energy calculations for the band gap, effective masses and deformation potentials of ScN
• Beyond the GW approximation: combining correlation channels
• Neutral and charged excitations in carbon fullerenes from first-principles many-body theories
• Elimination of the linearization error in GW calculations based on the linearized augmented-plane-wave method
• Optical spectra and exchange-correlation effects in molecular crystals
• Quantitative Molecular Orbital Energies within a $G_0{W}_0$ Approximation
• Many-body electronic structure and Kondo properties of cobalt-porphyrin molecules
• Ab initio complex band structure of conjugated polymers: Effects of hydrid DFT and GW schemes
• Anomalous molecular orbital variation upon adsorption on wide band gap insulator

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