Richardson-Gaudin states of non-zero seniority III: The Perfect-Pairing limit

Abstract

Strongly correlated electrons can be treated with a configuration interaction of Slater determinants grouped by number of unpaired electrons with exponential cost. The first two papers in this series demonstrated that single reference methods built from Richardson-Gaudin states gave results of similar quality at polynomial cost. In this contribution, the states are simplified substantially yielding the perfect-pairing state as a reference along with its low-lying excitations. The states are much simpler, the computational cost is substantially reduced, and there is no sacrifice in numerical accuracy. Second-order Epstein-Nesbet perturbative corrections for the valence electrons are similar in quality to the complete active space self-consistent field.