Quantitative Molecular Orbital Energies within a $G_0{W}_0$ Approximation

Abstract

Using many-body perturbation theory within the $G_0{W}_0$ approximation, we explore routes for computing the ionization potential (IP), electron affinity (EA), and fundamental gap of three gas-phase molecules -- benzene, thiophene, and (1,4) diamino-benzene -- and compare with experiments. We examine the dependence of the IP on the number of unoccupied states used to build the dielectric function and the self energy, as well as the dielectric function plane-wave cutoff. We find that with an effective completion strategy for approximating the unoccupied subspace, and a converged dielectric function kinetic energy cutoff, the computed IPs and EAs are in excellent quantitative agreement with available experiment (within 0.2 eV), indicating that a one-shot $G_0{W}_0$ approach can be very accurate for calculating addition/removal energies of small organic molecules. Our results indicate that a sufficient dielectric function kinetic energy cutoff may be the limiting step for a wide application of $G_0{W}_0$ to larger organic systems.

References in corpus (17)

• BerkeleyGW: A Massively Parallel Computer Package for the Calculation of the Quasiparticle and Optical Properties of Materials and Nanostructures
• Resolution-of-identity approach to Hartree-Fock, hybrid density functionals, RPA, MP2, and \textit{GW} with numeric atom-centered orbital basis functions
• First-principles GW calculations for fullerenes, porphyrins, phtalocyanine, and other molecules of interest for organic photovoltaic applications
• Ab initio GW many-body effects in graphene
• Fully selfconsistent GW calculations for molecules
• Quasiparticle and Optical Properties of Rutile and Anatase TiO${}_2$
• Quasiparticle and Optical Spectroscopy of Organic Semiconductors Pentacene and PTCDA from First Principles
• GW quasi-particle spectra from occupied states only
• Charge-transfer excitations in molecular donor-acceptor complexes within the many-body Bethe-Salpeter approach
• First-principles GW calculations for DNA and RNA nucleobases
• GW method with the self-consistent Sternheimer equation
• Self-Consistent Calculation of Total Energies of the Electron Gas Using Many-Body Perturbation Theory
• Electronic energy level alignment at metal-molecule interfaces with a GW approach
• Elimination of unoccupied state summations in ab-initio self-energy calculations for large supercells
• Enhanced Static Approximation to the Electron Self-Energy Operator for Efficient Calculation of Quasiparticle Energies
• Many-body GW Calculations of Ground-State Properties: Quasi-2D Electron Systems and van der Waals Forces
• Photoelectron properties of DNA and RNA bases from many-body perturbation theory

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