English

Singlet Geminal Wavefunctions

Chemical Physics 2024-10-03 v1

Abstract

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 dd- or ff-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.

Keywords

Cite

@article{arxiv.2410.01761,
  title  = {Singlet Geminal Wavefunctions},
  author = {Paul A. Johnson and Jean-David Moisset and Marianne Gratton and Émile Baril and Marc-Antoine Plourde and Mathis Lefebvre and Marianne Kerleaux and Paul W. Ayers and Patrick Cassam-Chenaï and Stijn De Baerdemacker and Dimitri Van Neck},
  journal= {arXiv preprint arXiv:2410.01761},
  year   = {2024}
}