Quasiparticle spectra from a non-empirical optimally-tuned range-separated hybrid density functional

Abstract

We present a method for obtaining outer valence quasiparticle excitation energies from a DFT-based calculation, with accuracy that is comparable to that of many-body perturbation theory within the GW approximation. The approach uses a range-separated hybrid density functional, with asymptotically exact and short-range fractional Fock exchange. The functional contains two parameters - the range separation and the short-range Fock fraction. Both are determined non-empirically, per system, based on satisfaction of exact physical constraints for the ionization potential and many-electron self-interaction, respectively. The accuracy of the method is demonstrated on four important benchmark organic molecules: perylene, pentacene, 3,4,9,10-perylene-tetracarboxylic-dianydride (PTCDA) and 1,4,5,8-naphthalene-tetracarboxylic dianhydride (NTCDA). We envision that for finite systems the approach could provide an inexpensive alternative to GW, opening the door to the study of presently out of reach large-scale systems.

References in corpus (8)

• Localization and delocalization errors in density functional theory and implications for band-gap prediction
• BerkeleyGW: A Massively Parallel Computer Package for the Calculation of the Quasiparticle and Optical Properties of Materials and Nanostructures
• Fractional charge perspective on the band-gap in density-functional theory
• First-principles GW calculations for fullerenes, porphyrins, phtalocyanine, and other molecules of interest for organic photovoltaic applications
• Polaronic hole localization and multiple hole binding of acceptors in oxide wide-gap semiconductors
• Koopmans' condition for density-functional theory
• Band convergence and linearization error correction of all-electron GW calculations: The extreme case of zinc oxide
• Quantitative Molecular Orbital Energies within a $G_0{W}_0$ Approximation

Cited by in corpus (57)

• NWChem: Past, Present, and Future
• The GW compendium: A practical guide to theoretical photoemission spectroscopy
• Identifying substitutional oxygen as a prolific point defect in monolayer transition metal dichalcogenides with experiment and theory
• Solid-state optical absorption from optimally-tuned time-dependent range-separated hybrid density functional theory
• Nonempirical Range-separated Hybrid Functionals for Solids and Molecules
• Breaking the theoretical scaling limit for predicting quasi-particle energies: The stochastic GW approach
• Piecewise Linearity of Approximate Density Functionals Revisited: Implications for Frontier Orbital Energies
• Koopmans-compliant functionals and their performance against reference molecular data
• An assessment of the low-lying excitation energies and triplet instabilities of organic molecules with an ab initio Bethe-Salpeter equation approach
• Evaluating the GW Approximation with CCSD(T) for Charged Excitations Across the Oligoacenes
• Shedding Light on Moire Excitons: A First-Principles Perspective
• Tuning Range-Separated Density Functional Theory for Photocatalytic Water Splitting Systems
• Experimental and theoretical electronic structure of quinacridone
• The Importance of Short- and Long-Range Exchange on Various Excited State Properties of DNA Monomers, Stacked Complexes, and Watson-Crick Pairs
• Energy Level Alignment at Molecule-Metal Interfaces from an Optimally-Tuned Range-Separated Hybrid Functional
• A self-interaction-free local hybrid functional: Accurate binding energies vis-à-vis accurate ionization potentials from Kohn-Sham eigenvalues
• One-electron self-interaction and the asymptotics of the Kohn-Sham potential: an impaired relation
• Interface dipoles of organic molecules on Ag(111) in hybrid density-functional theory
• Tracing orbital images on ultrafast time scales
• Ab Initio Bethe-Salpeter Equation Approach to Neutral Excitations in Molecules with Numeric Atom-Centered Orbitals
• Green's function methods for single molecule junctions
• Theoretical unification of hybrid-DFT and DFT+U methods for the treatment of localized orbitals
• Koopmans-compliant spectral functionals for extended systems
• Recovering the flat-plane condition in electronic structure theory at semi-local DFT cost
• Fundamental Principles for Calculating Charged Defect Ionization Energies in Ultrathin Two-Dimensional Materials
• Unified formulation of fundamental and optical gap problems in density-functional theory for ensembles
• A general range-separated double-hybrid density-functional theory
• Density Functional Theory for Electronic Excited States
• Resonant hot charge-transfer excitations in fullerene-porphyrin complexes: a many-body Bethe-Salpeter study
• Density-Dependent Onset of the Long-Range Exchange: A Key to Donor-Acceptor Properties
• Koopmans-compliant functionals and potentials and their application to the GW100 test-set
• Triplet Excitons and associated Efficiency-Limiting Pathways in Organic Solar Cell Blends based on (Non-) Halogenated PBDB-T and Y-Series
• An Optimally-Tuned Starting Point for Single-Shot $GW$ Calculations of Solids
• Exploring the Statically Screened $G3W2$ Correction to the $GW$ Self-Energy: Charged Excitations and Total Energies of Finite Systems
• The derivative discontinuity in the strong-interaction limit of density functional theory
• Spin-Conserved and Spin-Flip Optical Excitations From the Bethe-Salpeter Equation Formalism
• Transferable screened range-separated hybrid functionals for electronic and optical properties of van der Waals materials
• Nonequilibrium diagrammatic technique for Hubbard Green functions
• Accurate non-empirical range-separated hybrid van der Waals density functional for complex molecular problems, solids, and surfaces
• Screening in orbital-density-dependent functionals
• Beyond quasi-particle self-consistent $GW$ for molecules with vertex corrections
• vdW-DF-ahcx: a range-separated van der Waals density functional hybrid
• Learning the energy curvature versus particle number in approximate density functionals
• Excitons in InP, GaP, GaInP quantum dots: Insights from time-dependent density functional theory
• Charge transfer energies of benzene physisorbed on a graphene sheet from constrained density functional theory
• Density functional descriptions of interfacial electronic structure
• Renormalized Singles with Correlation in $GW$ Green's Function Theory for Accurate Quasiparticle Energies
• Simulating nuclear and electronic quantum effects in enzymes
• Valence-shell photoelectron circular dichroism of ruthenium(iii)-tris-(acetylacetonato) gas-phase enantiomers
• Hybrid functionals for periodic systems in the density functional tight-binding method
• Embedding vertex corrections in GW self-energy: theory, implementation, and outlook
• Employing Range Separation on the meta-GGA Rung: New Functional Suitable for Both Covalent and Noncovalent Interactions
• Hybrid-DFT+V${}_w$ method for accurate band structure of correlated transition metal compounds: the case of cerium dioxide
• Topological transitions to Weyl states in bulk Bi${}_2$Se${}_3$: Effect of hydrostatic pressure and doping
• Nature of frontier quasi-particle states in nitrogen-base systems
• 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