Chemical bonding theories as guides for self-interaction corrected solutions: Multiple local minima and symmetry breaking

• DOI: 10.1063/5.0071796
• Publication Date: 2021-11-22T16:36:25Z
• Authors: Kai Trepte; Sebastian Schwalbe; Simon Liebing; Wanja T. Schulze; Jens Kortus; Hemanadhan Myneni; Aleksei V. Ivanov; Susi Lehtola
• Keywords: Maxima and minima

Fermi-Löwdin orbitals (FLOs) are a special set of localized orbitals, which have become commonly used in combination with the Perdew-Zunger self-interaction correction (SIC) FLO-SIC method. The FLOs obtained for occupied by specifying classical position each electron. These positions known as Fermi-orbital descriptors (FODs), and they clear relation to chemical bonding. In this study, we show how FODs can be initialize, interpret, justify SIC solutions common picture, both within traditional variational SIC, locate distinct local minima either these approaches. We demonstrate that based on Lewis theory lead symmetry breaking benzene-the electron density is found break already at symmetric molecular structure-while ones from Linnett's double-quartet reproduce densities geometries. Introducing benchmark 16 planar cyclic molecules, using starting point artifactual dipole moments up 1 D, while Linnett better agreement experimental values. suggest moment diagnostic monitoring it all calculations. structures often seen superpositions propose simple way describe aromatic systems reduced breaking. role hovering also briefly discussed.