Density matrices of seniority-zero geminal wavefunctions.

Abstract

Scalar products and density matrix elements of closed-shell pair geminal wavefunctions are evaluated directly in terms of the pair amplitudes, resulting in an analog of Wick's theorem for fermions or bosons. This expression is, in general, intractable, but it is shown how it becomes feasible in three distinct ways for Richardson-Gaudin (RG) states, the antisymmetrized geminal power, and the antisymmetrized product of strongly orthogonal geminals. Dissociation curves for hydrogen chains are computed with off-shell RG states and the antisymmetrized product of interacting geminals. Both are near exact, suggesting that the incorrect results observed with ground state RG states (a local maximum rather than smooth dissociation) may be fixable using a different RG state.