Excitation energies from Görling–Levy perturbation theory along the range-separated adiabatic connection. (3rd June 2018)

• Record Type: Journal Article
• Authors: Rebolini, Elisa; Teale, Andrew M.; Helgaker, Trygve; Savin, Andreas; Toulouse, Julien
• Is Part Of: Molecular physics. Volume 116:Number 11(2018)
• Page Start: 1443
• Page End: 1451
• Publication Date: 2018-06-03
• Subjects: Density-functional theory -- range separation -- adiabatic connection -- perturbation theory -- excitation energies; Molecules -- Periodicals; Chemistry, Physical and theoretical -- Periodicals; Molécules -- Périodiques; Chimie physique et théorique -- Périodiques; 539.6.05
• DOI: 10.1080/00268976.2017.1422811
• Languages: English
• ISSNs: 0026-8976

Abstract

ABSTRACT: A Görling–Levy (GL)-based perturbation theory along the range-separated adiabatic connection is assessed for the calculation of electronic excitation energies. In comparison with the Rayleigh–Schrödinger (RS)-based perturbation theory this GL-based perturbation theory keeps the ground-state density constant at each order and thus gives the correct ionisation energy at each order. Excitation energies up to first order in the perturbation have been calculated numerically for the helium and beryllium atoms and the hydrogen molecule without introducing any density-functional approximations. In comparison with the RS-based perturbation theory, the present GL-based perturbation theory gives much more accurate excitation energies for Rydberg states but similar excitation energies for valence states. Abstract :