The time-dependent Hartree-Fock (TDHF) vertex of many-body perturbation theory (MBPT) makes it possible to extend TDHF theory to charged excitations. Here we assess its performance by applying it to spherical atoms in their neutral electronic configuration. On a theoretical level, we recast the TDHF vertex as a reducible vertex, highlighting the emergence of a self-energy expansion purely in orders of the bare Coulomb interaction; then, on a numerical level, we present results for polarizabilities, ionization energies (IEs), and photoemission satellites. We confirm the superiority of THDF over simpler methods such as the random phase approximation for the prediction of atomic polarizabilities. We then find that the TDHF vertex reliably provides better IEs than GW and low-order self-energies do in the light-atom, few-electron regime; its performance degrades in heavier, many-electron atoms instead, where an expansion in orders of an unscreened Coulomb interaction becomes less justified. New relevant features are introduced in the satellite spectrum by the TDHF vertex, but the experimental spectra are not fully reproduced due to a missing account of nonlinear effects connected to hole relaxation. We also explore various truncations of the self-energy given by the TDHF vertex, but do not find them to be more convenient than low-order approximations such as GW and second Born (2B), suggesting that vertex corrections should be carried out consistently both in the self-energy and in the polarizability.
Going Beyond the GW Approximation Using the Time-Dependent Hartree-Fock Vertex / Vacondio, S.; Varsano, D.; Ruini, A.; Ferretti, A.. - In: JOURNAL OF CHEMICAL THEORY AND COMPUTATION. - ISSN 1549-9618. - 20:11(2024), pp. 4718-4737. [10.1021/acs.jctc.4c00100]
Going Beyond the GW Approximation Using the Time-Dependent Hartree-Fock Vertex
Vacondio S.;Ruini A.Funding Acquisition
;
2024
Abstract
The time-dependent Hartree-Fock (TDHF) vertex of many-body perturbation theory (MBPT) makes it possible to extend TDHF theory to charged excitations. Here we assess its performance by applying it to spherical atoms in their neutral electronic configuration. On a theoretical level, we recast the TDHF vertex as a reducible vertex, highlighting the emergence of a self-energy expansion purely in orders of the bare Coulomb interaction; then, on a numerical level, we present results for polarizabilities, ionization energies (IEs), and photoemission satellites. We confirm the superiority of THDF over simpler methods such as the random phase approximation for the prediction of atomic polarizabilities. We then find that the TDHF vertex reliably provides better IEs than GW and low-order self-energies do in the light-atom, few-electron regime; its performance degrades in heavier, many-electron atoms instead, where an expansion in orders of an unscreened Coulomb interaction becomes less justified. New relevant features are introduced in the satellite spectrum by the TDHF vertex, but the experimental spectra are not fully reproduced due to a missing account of nonlinear effects connected to hole relaxation. We also explore various truncations of the self-energy given by the TDHF vertex, but do not find them to be more convenient than low-order approximations such as GW and second Born (2B), suggesting that vertex corrections should be carried out consistently both in the self-energy and in the polarizability.Pubblicazioni consigliate
I metadati presenti in IRIS UNIMORE sono rilasciati con licenza Creative Commons CC0 1.0 Universal, mentre i file delle pubblicazioni sono rilasciati con licenza Attribuzione 4.0 Internazionale (CC BY 4.0), salvo diversa indicazione.
In caso di violazione di copyright, contattare Supporto Iris