General Approach for Multireference Ground and Excited States Using Nonorthogonal Configuration Interaction.

Abstract

A balanced description of ground and excited states is essential for the description of many chemical processes. However, few methods can handle cases where static correlation is present, and often these scale very unfavorably with system size. Recently, multiple Hartree-Fock (HF) solutions have been proposed as a basis for nonorthogonal configuration interaction (NOCI) to provide multireference ground- and excited-state energies, although applications across multiple geometries have been limited by the coalescence of HF solutions. Holomorphic HF (h-HF) theory allows solutions to be analytically continued beyond the Coulson-Fischer points at which they vanish, but, until now, this has only been demonstrated for small model systems. In this work, we propose a general protocol for computing NOCI ground- and excited-state energies using multiple HF solutions. To do so, we outline an active space variation of SCF metadynamics that allows a chemically relevant set of HF states to be identified and describe how these states can be routinely traced across all molecular geometries by exploiting the topology of h-HF solutions in the complex plane. Finally, we illustrate our approach using the dissociation of the fluorine dimer and the pseudo-Jahn-Teller distortion of cyclobutadiene, demonstrating its applicability for multireference ground and excited states.