The GW Miracle in Many-Body Perturbation Theory for the Ionization Potential of Molecules.
Front Chem
; 9: 749779, 2021.
Article
em En
| MEDLINE
| ID: mdl-35004607
ABSTRACT
We use the GW100 benchmark set to systematically judge the quality of several perturbation theories against high-level quantum chemistry methods. First of all, we revisit the reference CCSD(T) ionization potentials for this popular benchmark set and establish a revised set of CCSD(T) results. Then, for all of these 100 molecules, we calculate the HOMO energy within second and third-order perturbation theory (PT2 and PT3), and, GW as post-Hartree-Fock methods. We found GW to be the most accurate of these three approximations for the ionization potential, by far. Going beyond GW by adding more diagrams is a tedious and dangerous activity We tried to complement GW with second-order exchange (SOX), with second-order screened exchange (SOSEX), with interacting electron-hole pairs (W TDHF), and with a GW density-matrix (γ GW ). Only the γ GW result has a positive impact. Finally using an improved hybrid functional for the non-interacting Green's function, considering it as a cheap way to approximate self-consistency, the accuracy of the simplest GW approximation improves even more. We conclude that GW is a miracle Its subtle balance makes GW both accurate and fast.
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Coleções:
01-internacional
Base de dados:
MEDLINE
Idioma:
En
Revista:
Front Chem
Ano de publicação:
2021
Tipo de documento:
Article
País de afiliação:
França