Benchmarking GW against exact diagonalization for semiempirical models

Kristen Kaasbjerg, Kristian Sommer Thygesen

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Abstract

We calculate ground-state total energies and single-particle excitation energies of seven pi-conjugated molecules described with the semiempirical Pariser-Parr-Pople model using self-consistent many-body perturbation theory at the GW level and exact diagonalization. For the total energies GW captures around 65% of the ground-state correlation energy. The lowest lying excitations are overscreened by GW leading to an underestimation of electron affinities and ionization potentials by 0.15 eV on average corresponding to ∼3%. One-shot G0W0 calculations starting from Hartree-Fock reduce the screening and improve the low-lying excitation energies. The effect of the GW self-energy on the molecular excitation energies is shown to be similar to the inclusion of final-state relaxations in Hartree-Fock theory. We discuss the breakdown of the GW approximation in systems with short-range interactions (Hubbard models) where correlation effects dominate over screening/relaxation effects. Finally we illustrate the important role of the derivative discontinuity of the true exchange-correlation functional by computing the exact Kohn-Sham levels of benzene.
Original languageEnglish
JournalPhysical Review B Condensed Matter
Volume81
Issue number8
Pages (from-to)085102
ISSN0163-1829
DOIs
Publication statusPublished - 2010

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Copyright 2010 American Physical Society

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