Effects of self-consistency and plasmon-pole models on GW calculations for closed-shell molecules

Abstract

We present theoretical calculations of quasiparticle energies in closed-shell molecules using the GW method. We compare three different approaches: a full-frequency $G_0{W}_0$ (FF-$G_0{W}_0$) method with density functional theory (DFT-PBE) used as a starting mean field; a full-frequency $G{W}_0$ (FF-$G{W}_0$) method where the interacting Green's function is approximated by replacing the DFT energies with self-consistent quasiparticle energies or Hartree-Fock energies; and a $G_0{W}_0$ method with a Hybertsen-Louie generalized plasmon-pole model (HL GPP-$G_0{W}_0$). While the latter two methods lead to good agreement with experimental ionization potentials and electron affinities for methane, ozone, and beryllium oxide molecules, FF-$G_0{W}_0$ results can differ by more than one electron volt from experiment. We trace this failure of the FF-$G_0{W}_0$ method to the occurrence of incorrect self-energy poles describing shake-up processes in the vicinity of the quasiparticle energies.

arXiv comment6 pages, 4 figures, accepted to Phys. Rev. B

References in corpus (18)

• Quantum ESPRESSO: a modular and open-source software project for quantum simulations of materials
• BerkeleyGW: A Massively Parallel Computer Package for the Calculation of the Quasiparticle and Optical Properties of Materials and Nanostructures
• Renormalization of Molecular Electronic Levels at Metal-Molecule Interfaces
• First-principles GW calculations for fullerenes, porphyrins, phtalocyanine, and other molecules of interest for organic photovoltaic applications
• Truncation of Periodic Image Interactions for Confined Systems
• Fully selfconsistent GW calculations for molecules
• Quasiparticle GW calculations for solids, molecules and 2D materials
• Unified description of ground and excited states of finite systems: the self-consistent GW approach
• Optical excitations in organic molecules, clusters and defects studied by first-principles Green's function methods
• Renormalization of Molecular Quasiparticle Levels at Metal-Molecule Interfaces: Trends Across Binding Regimes
• High Accuracy Many-Body Calculational Approaches for Excitations in Molecules
• Coulomb-hole summations and energies for GW calculations with limited number of empty orbitals: a modified static remainder approach
• Levels of self-consistency in the GW approximation
• The valence electron photoemission spectrum of semiconductors: ab initio description of multiple satellites
• Physical origin of satellite in photoemission of doped graphene: An ab-initio GW plus cumulant study
• An O(N^3) implementation of Hedin's GW approximation for molecules
• Quantitative Molecular Orbital Energies within a $G_0{W}_0$ Approximation
• First-principles calculations of the electronic structure of open-shell condensed matter systems

Cited by in corpus (6)

• Quasi-Particle Self-Consistent $GW$ for Molecules
• Structural and excited-state properties of oligoacene crystals from first principles
• Evaluating the GW Approximation with CCSD(T) for Charged Excitations Across the Oligoacenes
• Cubic-scaling all-electron GW calculations with a separable density-fitting space-time approach
• Frequency dependence in GW made simple using a multi-pole approximation
• Fully Analytic Nuclear Gradients for the Bethe--Salpeter Equation