Excitation energies from Görling–Levy perturbation theory along the range-separated adiabatic connection

Rebolini, Elisa and Teale, Andrew M. and Helgaker, Trygve and Savin, Andreas and Toulouse, Julien (2018) Excitation energies from Görling–Levy perturbation theory along the range-separated adiabatic connection. Molecular Physics, 116 (11). pp. 1443-1451. ISSN 1362-3028

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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.

Item Type: Article
Additional Information: This is an Accepted Manuscript of an article published by Taylor & Francis in Molecular Physics on 15 January 2018, available online: http://www.tandfonline.com/10.1080/00268976.2017.1422811.
Keywords: Density-functional theory, range separation, adiabatic connection, perturbation theory, excitation energies
Schools/Departments: University of Nottingham, UK > Faculty of Science > School of Chemistry
Identification Number: https://doi.org/10.1080/00268976.2017.1422811
Depositing User: Teale, Andrew
Date Deposited: 28 Mar 2018 13:50
Last Modified: 27 Jun 2018 09:32
URI: http://eprints.nottingham.ac.uk/id/eprint/50764

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