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The GW Miracle in Many-Body Perturbation Theory for the Ionization Potential of Molecules.


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.

SUBMITTER: Bruneval F 

PROVIDER: S-EPMC8733722 | biostudies-literature | 2021

REPOSITORIES: biostudies-literature

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The GW Miracle in Many-Body Perturbation Theory for the Ionization Potential of Molecules.

Bruneval Fabien F   Dattani Nike N   van Setten Michiel J MJ  

Frontiers in chemistry 20211221


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, <i>GW</i> as post-Hartree-Fock methods. We found <i>GW</i> to be the  ...[more]

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