Do Dyson Orbitals resemble canonical Hartree–Fock orbitals?

ABSTRACT

Dyson orbitals are overlaps between states with N and N±1 electrons and provide conceptual links between transition probabilities of electron detachment or attachment, density matrices, total energies and general principles of chemical bonding. Canonical, Hartree–Fock orbitals are compared with Dyson orbitals obtained with electron–propagator calculations that retain all elements of the self–energy matrix, wherein all orbital–relaxation and electron–correlation corrections to Koopmans results reside. For valence ionization energies and electron affinities of representative closed–shell molecules, canonical, Hartree–Fock orbitals usually are excellent approximations to Dyson orbitals, although there are some notable cases where the resemblance is not as strong. Numerical relationships between pole strengths and the Koopmans contributions to Dyson orbitals also are inferred from the data.

GRAPHICAL ABSTRACT

KEYWORDS:

• Electron propagator
• Dyson orbitals
• electron affinities
• ionization energies
• Feynman–Dyson amplitudes

Disclosure statement

No potential conflict of interest was reported by the authors.

Additional information

Funding

The National Science Foundation supported this research through grant CHE-1565760 to Auburn University.