Singlet Geminal Wavefunctions

Creators: Johnson, Paul; Moisset, Jean-David; Gratton, Marianne; Baril, Émile; Plourde, Marc-Antoine; Lefebvre, Mathis; Kerleaux, Marianne; Ayers, Paul; Cassam-Chenaï, Patrick; de Baerdemacker, Stijn; van Neck, Dimitri

Others:: Département de chimie [Laval-Québec] ; Université Laval [Québec] (ULaval)-Faculté des sciences et de génie [Laval-Québec] (FSG) ; Université Laval [Québec] (ULaval); McMaster University [Hamilton, Ontario]; Laboratoire Jean Alexandre Dieudonné (LJAD) ; Université Nice Sophia Antipolis (1965 - 2019) (UNS)-Centre National de la Recherche Scientifique (CNRS)-Université Côte d'Azur (UniCA); University of New Brunswick (UNB); Universiteit Gent = Ghent University (UGENT)

Description

Wavefunction forms based on products of electron pairs are usually constructed as closed-shell singlets, which is insufficient when the molecular state has a nonzero spin or when the chemistry is determined by $d$- or $f-$electrons. A set of two-electron forms are considered as explicit couplings of second-quantized operators to open-shell singlets. Geminal wavefunctions are constructed and their structure is elaborated. Numerical results for small model systems clearly demonstrate improvement over closed-shell singlet pairs.

Singlet Geminal Wavefunctions

Description

Additional details