Selected configuration interaction for high accuracy and compact wave functions: Propane as a case study

Abstract

Traditionally, because of the limit of full configuration interaction, complete active space (CAS) theory is most often used to model bond dissociation and other dynamical processes where the multi-reference character becomes important. Inconveniently, the CAS method is highly dependent on the choice of active space and, therefore, inherently non-black-box, in addition to the exponential scaling with respect to electrons and orbitals. This illustrates the need for methods that can accurately treat multi-reference electronic structure problems without significant dependence on input parameters. Selected configuration interaction (SCI) methods have experienced a revival in recent years because of their independence of these predicaments. SCI methods aim to exploit the sparsity of the full configuration interaction space to identify all relevant electronic configurations and, therefore, keep the wave function as compact as possible while still representing the total multi-reference electronic structure accurately. In this work, we take the recent achievement by Gao et al. to run full configuration interaction on the propane molecule in a minimal basis set (23 electrons in 26 orbitals) as an occasion to demonstrate that our SCI methods implemented in the GeneralSCI program package can achieve high energetic accuracy in conjunction with very compact wave functions, which considerably alleviate computational cost. Furthermore, we show the good performance of our SCI methods in reproducing a propane bond dissociation surface and energy. This illustrates that SCI methods can be readily applied to problems in chemical reactivity.