Ab Initio Electron Propagators with an Hermitian, Intermediately Normalized Superoperator Metric Applied to Vertical Electron Affinities.

ABSTRACT

New-generation ab initio electron propagator methods for calculating electron detachment energies of closed-shell molecules and anions have surpassed their predecessors' accuracy and computational efficiency. Derived from an Hermitian, intermediately normalized superoperator metric, these methods contain no adjustable parameters. To assess their versatility, a standard set (NIST-50-EA) of 50 vertical electron affinities of small closed-shell molecules based on NIST reference data has been created. Errors with respect to reference data on 23 large, conjugated organic photovoltaic (OPV23) molecules have also been analyzed. All final states are valence anions that correspond to electron affinities between 0.2 and 4.2 eV. For a given scaling of the arithmetic bottleneck, the new-generation methods obtain the lowest mean absolute errors (MAEs). The best methods with fifth-power arithmetic scaling realize MAEs below 0.1 eV. Composite models comprising cubically and quintically scaling calculations executed with large and small basis sets, respectively, produce OPV23 MAEs near 0.05 eV. The accuracy of quintically scaling methods executed with large basis sets is thereby procured with reduced computational effort. New-generation results obtained with and without the diagonal self-energy approximation in the canonical Hartree-Fock basis have been compared. These results indicate that Dyson orbitals closely resemble canonical Hartree-Fock orbitals multiplied by the square root of a probability factor above 0.85.