New-Generation Electron-Propagator Methods for Calculations of Electron Affinities and Ionization Energies: Tests on Organic Photovoltaic Molecules.

ABSTRACT

A new generation of ab initio electron-propagator self-energies recently superseded its antecedents' accuracy and computational efficiency in calculating vertical ionization energies (VIEs) of closed-shell molecules. (See J. Chem. Phys. 2021, 155, 204107, J. Chem. Theory Comput. 2022, 18, 4927, J. Chem. Phys. 2023, 159, 124109.) No adjustable parameters were introduced in the generation of reference orbitals or in the construction of self-energies. The same approach has been extended in this work to vertical electron affinities (VEAs). Calculations were performed on 24 conjugated, organic photovoltaic molecules with diverse functional groups. These molecules are considerably larger than those studied in previous tests on VIEs. Several new-generation self-energies produce mean absolute errors (MAEs) below 0.1 eV versus ΔCCSD(T) (i.e., total energy differences from the coupled-cluster singles, doubles, and perturbative triples method) VIEs and VEAs obtained with identical basis sets. A composite model employs cubically and quintically scaling algorithms and power-law basis-set extrapolations based on augmented double-triple or triple-quadruple ζ data. Its MAEs are near 0.05 eV versus benchmark values, with 0.03 eV error bars for the lowest VIE and the highest VEA of each molecule. A more efficient and equally accurate composite model for calculating VIEs avoids full transformations of electron repulsion integrals to the molecular orbital basis. High probability factors support the diagonal self-energy approximation, wherein Dyson orbitals are proportional to canonical, Hartree-Fock orbitals.