RPAx Instabilities from Ground- and Excited-State References

Abstract

Random-phase approximation with exchange (RPAx) calculations based on ground- or excited-state references can yield complex excitation energies, causing the corresponding RPAx correlation energy to become complex as well. In this work, we investigate the origin of these complex energies using \ce{H2} in the 6-31G basis set as a minimal model. For the ground-state restricted Hartree-Fock reference, complex roots emerge at the well-known triplet instability associated with the appearance of a lower-lying unrestricted, symmetry-broken solution. For excited-state references, we identify two distinct mechanisms leading to complex excitation energies. The first is similarly associated with symmetry breaking. The second arises when a positive-energy excitation becomes degenerate with the positive-energy de-excitation associated with a negative-energy transition. Finally, we demonstrate the practical implications of these findings for spin-flip Bethe-Salpeter equation calculations of cyclobutadiene and state-specific core-ionization calculations for selected systems. These examples show that, in the absence of the relevant instabilities, methods sharing the generalized eigenvalue structure of RPAx can be applied to excited-state references without resorting to the Tamm-Dancoff or core-valence separation approximations, while retaining real excitation energies.