Hartree-Fock symmetry breaking around conical intersections

Abstract

We study the behavior of Hartree-Fock (HF) solutions in the vicinity of conical intersections. These are here understood as regions of a molecular potential energy surface characterized by degenerate or nearly degenerate eigenfunctions with identical quantum numbers (point group, spin, and electron numbers). Accidental degeneracies between states with different quantum numbers are known to induce symmetry breaking in HF. The most common closed-shell restricted HF instability is related to singlet-triplet spin degeneracies that lead to collinear unrestricted HF solutions. Adding geometric frustration to the mix usually results in noncollinear generalized HF (GHF) solutions, identified by orbitals that are linear combinations of up and down spins. Near conical intersections, we observe the appearance of coplanar GHF solutions that break all symmetries, including complex conjugation and time-reversal, which do not carry good quantum numbers. We discuss several prototypical examples taken from the conical intersection literature. Additionally, we utilize a recently introduced magnetization diagnostic to characterize these solutions, as well as a solution of a Jahn-Teller active geometry of H8+2.