Electron binding energies and Dyson orbitals generated in ab initio, electron propagator calculations may be used to assign photoelectron spectra of molecular anions and their complexes with coordinating species. Dyson orbitals whose largest amplitudes lie far from the nuclear framework for electron detachment from diffuse-bound anions of nucleic-acid bases may acquire more valence character in the presence of polar or polarizable molecules or atoms. In some species, diffuse-bound and valence-bound anionic states are predicted.  Correlation terms in the self-energy of the Dyson equation can be chiefly responsible for the binding of electrons to molecules in excited, anionic states of fullerenes, especially in cases where Dyson orbitals for electron detachment are diffuse. In certain neutral and anionic metallo-macrocyclic compounds, strong correlation effects obliterate the Koopmans picture of electron binding energies and require renormalized self-energies for their description.

Dyson orbitals and electron binding energies of anionic nucleic-acid fragments, fullerenes, and macrocyclic compounds

248th National Meeting (2014)

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