Rationale for the extrapolation procedure in selected configuration interaction.

Abstract

Selected configuration interaction (SCI) methods have emerged as state-of-the-art methodologies for achieving high accuracy and generating benchmark reference data for ground and excited states in small molecular systems. However, their precision relies heavily on extrapolation procedures to produce a final estimate of the exact result. Using the structure of the exact electronic energy landscape, we provide a rationale for the common linear extrapolation of the variational energy as a function of the second-order perturbative correction. In particular, we demonstrate that the energy gap and the coupling between the so-called internal and external spaces are the key factors determining the rate at which the linear regime is reached. Starting from the first principles, we also derive a new non-linear extrapolation formula that improves the post-processing of data generated from SCI methods and can be applied to both ground- and excited-state energies.