Transformation to a geminal basis and stationary conditions for the exact wave function therein

Abstract

AbstractWe show the transformation from a one-particle basis to a geminal basis, transformations between different geminal bases demonstrate the Lie algebra of a geminal basis. From the basis transformations, we express both the wave function and Hamiltonian in the geminal basis. The necessary and sufficient conditions of the exact wave function expanded in a geminal basis are shown to be a Brillouin theorem of geminals. The variational optimization of the geminals in the antisymmetrized geminal power (AGP), antisymmetrized product of geminals (APG) and the full geminal product (FGP) wave function ansätze are discussed. We show that using a geminal replacement operator to describe geminal rotations introduce both primary and secondary rotations. The secondary rotations rotate two geminals in the reference at the same time due to the composite boson nature of geminals. Due to the completeness of the FGP, where all possible geminal combinations are present, the FGP is exact. The number of parameters in the FGP scale exponentially with the number of particles, like the full configuration interaction (FCI). Truncation in the FGP expansion can give compact representations of the wave function since the reference function in the FGP can be either the AGP or APG wave function.