Localized Spin Rotations: A Size-Consistent Approach to Nonorthogonal Configuration Interaction

Current nonorthogonal configuration interaction (NOCI) methods often use a set of self-consistent field (SCF) states selected based on chemical intuition. However, it may be challenging to track these SCF states across a dissociation profile and the NOCI states recovered may be spin contaminated. In this Article, we propose a method of applying spin rotation on symmetry broken unrestricted Hartree-Fock (sb-UHF) states to generate a basis for NOCI. The dissociation of ethene was examined by localizing spin rotation on each resulting carbene fragment. We show that this gives a size-consistent description of its dissociation and results in spin-pure states at all geometries. The dissociation was also studied with different orbitals, namely, canonical UHF and absolutely localized molecular orbitals (ALMO). Furthermore, we demonstrate that the method can be used to restore spin symmetry of symmetry broken SCF wave functions for molecules of various sizes, marking an improvement over existing NOCI methods.

Automated summary

In this article, a method of applying spin rotation on symmetry broken unrestricted Hartree-Fock (sb-UHF) states to generate a basis for nonorthogonal configuration interaction (NOCI) is proposed. The dissociation of ethene was examined using this method and spin-pure states were obtained. The method was also shown to restore spin symmetry for molecules of various sizes, improving upon existing NOCI methods.