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

TL;DR

This paper develops a mathematical framework for transforming and optimizing wave functions in a geminal basis, demonstrating the exactness of the Full Geminal Product and discussing potential for compact wave function representations.

Contribution

It introduces basis transformations, stationary conditions, and optimization methods for geminal-based wave functions, establishing the FGP as an exact representation.

Findings

The FGP is exact due to its completeness.

Geminal rotations include primary and secondary types.

Truncation of FGP may enable compact wave function approximations.

Abstract

We show the transformation from a one-particle basis to a geminal basis, transformations between different geminal bases and 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 is 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 ans{\"a}tze 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 could lead to compact representations of the wave function in the future since the reference function in the FGP is the APG wave function.