Localised Spin Rotations: A Size-Consistent Approach to Non-Orthogonal Configuration Interaction

TL;DR

This paper introduces a size-consistent, spin-pure NOCI method using localized spin rotations on symmetry-broken UHF states, improving dissociation descriptions and spin symmetry restoration across various molecules.

Contribution

It proposes a novel spin rotation approach on sb-UHF states for NOCI, enhancing size consistency and spin purity in molecular dissociation studies.

Findings

Achieves size-consistent dissociation of ethene with spin-pure states.

Restores spin symmetry in SCF wavefunctions for various molecules.

Demonstrates improved NOCI results over traditional methods.

Abstract

Current Non-Orthogonal 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 paper, we propose a method of applying spin rotation on symmetry broken UHF (sb-UHF) states to generate a basis for NOCI. The dissociation of ethene was examined by localising 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 Localised Molecular Orbitals (ALMO). Furthermore, we demonstrate that the method can be used to restore spin symmetry of symmetry broken SCF wavefunctions for molecules of various sizes, marking an improvement over existing NOCI methods.