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 (50)

• The GW method
• Quasiparticle Self-Consistent GW Theory
• Renormalization of Molecular Electronic Levels at Metal-Molecule Interfaces
• Resolution-of-identity approach to Hartree-Fock, hybrid density functionals, RPA, MP2, and \textit{GW} with numeric atom-centered orbital basis functions
• All-electron self-consistent GW approximation: Application to Si, MnO, and NiO
• 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
• Combining GW calculations with exact-exchange density-functional theory: An analysis of valence-band photoemission for compound semiconductors
• Fully selfconsistent GW calculations for molecules
• Self-Energy and Excitonic Effects in the Electronic and Optical Properties of TiO2 Crystalline Phases
• Polarization-induced renormalization of molecular levels at metallic and semiconducting surfaces
• Conserving GW scheme for nonequilibrium quantum transport in molecular contacts
• Unified description of ground and excited states of finite systems: the self-consistent GW approach
• Quasiparticle and Optical Spectroscopy of Organic Semiconductors Pentacene and PTCDA from First Principles
• GW quasi-particle spectra from occupied states only
• Renormalization of Molecular Quasiparticle Levels at Metal-Molecule Interfaces: Trends Across Binding Regimes
• Charge-transfer excitations in molecular donor-acceptor complexes within the many-body Bethe-Salpeter approach
• High Accuracy Many-Body Calculational Approaches for Excitations in Molecules
• First-principles GW calculations for DNA and RNA nucleobases
• Band convergence and linearization error correction of all-electron GW calculations: The extreme case of zinc oxide
• Levels of self-consistency in the GW approximation
• Band gap and band parameters of InN and GaN from quasiparticle energy calculations based on exact-exchange density-functional theory
• Many-body perturbation theory using the density-functional concept: beyond the GW approximation
• Fully self-consistent GW calculations for atoms and molecules
• Effect of Semicore Orbitals on the Electronic Band Gaps of Si, Ge, and GaAs within the GW Approximation
• Short to long-range charge-transfer excitations in the zincbacteriochlorin-bacteriochlorin complex: a Bethe-Salpeter study
• Renormalization of Optical Excitations in Molecules near a Metal Surface
• Exact-exchange based quasiparticle energy calculations for the band gap, effective masses and deformation potentials of ScN
• Ab initio GW electron-electron interaction effects in Quantum Transport
• Beyond the GW approximation: combining correlation channels
• All-electron GW calculation for molecules: Ionization energy and electron affinity of conjugated molecules
• 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
• Electronic energy level alignment at metal-molecule interfaces with a GW approach
• Optical spectra and exchange-correlation effects in molecular crystals
• First-principles GW-BSE excitations in organic molecules
• Quasiparticle Excitations and Charge Transition Levels of Oxygen Vacancies in Hafnia
• Quantitative Molecular Orbital Energies within a $G_0{W}_0$ Approximation
• Vertex corrections in localized and extended systems
• GW approach to Anderson model out of equilibrium: Coulomb blockade and false hysteresis in the I-V characteristics
• 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
• GW approximation with self-screening correction
• Approximations for many-body Green's functions: insights from the fundamental equations
• Image states in metal clusters
• Photoelectron properties of DNA and RNA bases from many-body perturbation theory
• Benchmarking GW against exact diagonalization for semi-empirical models
• GW approximations and vertex corrections on the Keldysh time-loop contour: application for model systems at equilibrium
• Anomalous molecular orbital variation upon adsorption on wide band gap insulator

Cited by in corpus (74)

• CP2K: An Electronic Structure and Molecular Dynamics Software Package -- Quickstep: Efficient and Accurate Electronic Structure Calculations
• The GW compendium: A practical guide to theoretical photoemission spectroscopy
• Self-consistent GW: All-electron implementation with localized basis functions
• Quasi-Particle Self-Consistent $GW$ for Molecules
• Breaking the theoretical scaling limit for predicting quasi-particle energies: The stochastic GW approach
• Towards GW Calculations on Thousands of Atoms
• Benchmark of GW approaches for the GW100 testset
• Accurate absolute and relative core-level binding energies from $GW$
• Fully self-consistent $GW$ and 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
• Low-order Scaling $G_0{W}_0$ by Pair Atomic Density Fitting
• Automation methodologies and large-scale validation for $GW$, towards high-throughput $GW$ calculations
• Accurate description of charged excitations in molecular solids from embedded many-body perturbation theory
• Interface dipoles of organic molecules on Ag(111) in hybrid density-functional theory
• Ab Initio Bethe-Salpeter Equation Approach to Neutral Excitations in Molecules with Numeric Atom-Centered Orbitals
• Many-body Green's function GW and Bethe-Salpeter study of the optical excitations in a paradigmatic model dipeptide
• All-electron periodic $G_0{W}_0$ implementation with numerical atomic orbital basis functions: algorithm and benchmarks
• Electronic Excitations in Complex Molecular Environments: Many-Body Green's Functions Theory in VOTCA-XTP
• First-Principles Description of Charge Transfer in Donor-Acceptor Compounds from Self-Consistent Many-Body Perturbation Theory
• Resonant hot charge-transfer excitations in fullerene-porphyrin complexes: a many-body Bethe-Salpeter study
• Fermi gas throughout the BCS-BEC crossover: Comparative study of t-matrix approaches with various degrees of self-consistency
• Quantum transport simulation scheme including strong correlations and its application to organic radicals adsorbed on gold
• Vertex corrections to the polarizability do not improve the GW approximation for the ionization potential of molecules
• Stochastic Optimally-Tuned Ranged-Separated Hybrid Density Functional Theory
• An Optimally-Tuned Starting Point for Single-Shot $GW$ Calculations of Solids
• Renormalized Singles Green's Function in the T-Matrix Approximation for Accurate Quasiparticle Energy Calculation
• Relativistic correction scheme for core-level binding energies from $GW$
• Reference Energies for Valence Ionizations and Satellite Transitions
• Piecewise linearity in the $GW$ approximation for accurate quasiparticle energy predictions
• A similarity renormalization group approach to Green's function methods
• Length Dependence of Ionization Potentials of Trans-Acetylenes: Internally-Consistent DFT/GW Approach
• The GW plus cumulant method and plasmonic polarons: application to the homogeneous electron gas
• Optical properties of azobenzene-functionalized self-assembled monolayers: Intermolecular coupling and many-body interactions
• Two-component $GW$ calculations: Cubic scaling implementation and comparison of vertex corrected and partially self-consistent $GW$ variants
• On the Possibility of Singlet Fission in Crystalline Quaterrylene
• Optical absorption spectra of metal oxides from time-dependent density functional theory and many-body perturbation theory based on optimally-tuned hybrid functionals
• Simple eigenvalue-self-consistent $\bar{\Delta }G{W}_0$
• Hubbard-$U$ corrected Hamiltonians for non-self-consistent random-phase approximation total-energy calculations: A study of ZnS, TiO${}_2$, and NiO
• Critical assessment of $G_0{W}_0$ calculations for 2D materials: the example of monolayer MoS${}_2$
• Linear Scaling Calculations of Excitation Energies with Active-Space Particle-Particle Random Phase Approximation
• Assessment of the Ab Initio Bethe-Salpeter Equation Approach for the Low-Lying Excitation Energies of Bacteriochlorophylls and Chlorophylls
• Wave-function inspired density functional applied to the H${}_2$/H${}_2^{+}$ challenge
• Can $GW$ Handle Multireference Systems?
• Quasi-particle energy spectra in local reduced density matrix functional theory
• Vertex effects in describing the ionization energies of the first-row transition-metal monoxide molecules
• Combining Localized Orbital Scaling Correction and Bethe-Salpeter Equation for Accurate Excitation Energies
• Probing the LDA-1/2 method as a starting point for $G_0{W}_0$ calculations
• Atomic photoionization cross-sections beyond the electric dipole approximation
• Renormalized Singles with Correlation in $GW$ Green's Function Theory for Accurate Quasiparticle Energies
• Efficient Full-frequency GW Calculations using a Lanczos Method
• X-ray absorption of liquid water by advanced ab initio methods
• Accurate ionization potential of gold anionic clusters from density functional theory and many-body perturbation theory
• Challenges with relativistic GW calculations in solids and molecules
• Practical $GW$ scheme for electronic structure of 3$d$-transition-metal monoxide anions: ScO${}^{-}$, TiO${}^{-}$, CuO${}^{-}$, and ZnO${}^{-}$
• Anomalous propagators and the particle-particle channel: Bethe-Salpeter equation
• Revisiting the homogeneous electron gas in pursuit of the properly normed ab initio Eliashberg theory
• Solvent effects on optical excitations of poly para phenylene ethynylene studied by QM/MM simulations based on Many-Body Green's Functions Theory
• Quasiparticle and fully self-consistent GW methods: an unbiased analysis using Gaussian orbitals
• GW with hybrid functionals for large molecular systems
• Joint Approximate Diagonalization approach to Quasiparticle Self-Consistent $GW$ calculations
• Photoelectron spectra of early $3d$-transition metal dioxide cluster anions from $GW$ calculations
• A simple many-body based screening optimization and mixing ansatz for improvement of GW/BSE excitation energies of molecular systems
• An investigation of the sensitivity of the Fermi surface to the treatment of exchange and correlation
• Full self-consistency versus quasiparticle self-consistency in diagrammatic approaches: Exactly solvable two-site Hubbard Model
• Parquet theory for molecular systems: Formalism and static kernel parquet approximation
• Stochastic GW calculations for molecules
• Polarizable Continuum Models and Green's Function $\mathbf{GW}$ Formalism: On the Dynamics of the Solvent Electrons
• Many-body perturbation theory with hybrid density functional theory starting points accelerated by adaptively compressed exchange
• Formation energy of intrinsic defects in silicon from the Galitskii-Migdal formula
• Implementation and benchmark of a long-range corrected functional in the density functional based tight-binding method
• Stochastic Resolution of Identity for Real-Time Second-Order Green's Function: Ionization Potential and Quasi-particle Spectrum
• All-electron Quasiparticle Self-consistent GW for Molecules and Periodic Systems within the Numerical Atomic Orbital Framework
• Many-body theory predictions of positron binding energies in five-membered heterocycles involving N, O, S and NH substituents