Seniority-zero states are mean-field wavefunctions
Abstract
We use symbolic computation, numerical experiments, and mathematical arguments to establish that every seniority-zero state can be expressed as a (number-symmetry-broken) antisymmetric product of interacting geminals (APIG). Moreover, for bosons, the configuration interaction coefficients are exactly parameterized by matrix permanents. This establishes that bosonic wavefunctions can be exactly described by a mean field, specifically the (number-symmetry-broken) symmetric product of boson orbitals. While exact parameterization is extremely costly, we present numerical evidence showing that the APIG wavefunction approaches the true wavefunction exponentially quickly as the number of interacting geminals increases.
Article Details
Journal Info
The Journal of Chemical Physics
American Institute of Physics
Authors (8)
Marco Martínez González
Department of Chemistry & Chemical Biology, McMaster University 1 , Hamilton, Ontario L8S 4M1,
Daniel F. Calero-Osorio
Department of Chemistry, McMaster University , Hamilton, Ontario L8S 4M1,
Michelle Richer
Department of Chemistry & Chemical Biology, McMaster University 1 , Hamilton, Ontario L8S 4M1,
Cassandra Masschelein
Department of Chemistry & Chemical Biology, McMaster University 1 , Hamilton, Ontario L8S 4M1,
Shuoyang Wang
Department of Chemistry & Chemical Biology, McMaster University 1 , Hamilton, Ontario L8S 4M1,
Paul A. Johnson
Département de Chimie, Université Laval 1 , Québec, Québec G1V 0A6,
Stijn De Baerdemacker
Department of Chemistry, University of New Brunswick 3 , Fredericton, New Brunswick E3B 5A3,
Paul W. Ayers
Chemistry and Chemical Biology, McMaster University 1 , Hamilton, Ontario L8S 4L8,