Exploring Dyson’s Orbitals and Their Electron Binding Energies for Conceptualizing Excited States from Response Methodology
Vladimir A. Pomogaev, Seunghoon Lee, Sason Shaik, Michael Filatov, Cheol Ho Choi
Abstract
, natural or natural transition orbitals. Because these orbitals lack the respective energies, they do not allow developing a consistent orbital picture of the excited states. Herein, we argue that Dyson's orbitals enable description of the response states compatible with the concepts of molecular orbital theory. The Dyson orbitals and their energies obtained by mixed-reference spin-flip time-dependent density functional theory (MRSF-TDDFT) for the response ground state are remarkably similar to the canonical MOs obtained by the usual DFT calculation. For excited states, the Dyson orbitals provide a chemically sensible picture of the electronic transitions, thus bridging the chasm between orbital theory and response computations.