Geminal-based electronic structure methods in quantum chemistry. Toward a geminal model chemistry

Abstract

In this review, we discuss the recent progress in developing geminal-based theories for challenging problems in quantum chemistry. Specifically, we focus on the antisymmetrized geminal power, generalized valence bond, antisymmetrized product of strongly orthogonal geminals, singlet-type orthogonal geminals, the antisymmetric product of 1-reference orbital geminal, also known as the pair coupled cluster doubles ansatz, and geminals constructed from Richardson–Gaudin states. Furthermore, we review various corrections to account for the missing dynamical correlation effects in geminal models and possible extensions to target electronically excited states and open-shell species. Finally, we discuss some numerical examples and present-day challenges for geminal-based models, including a quantitative and qualitative analysis of wave functions, and software availability.