title: Core ionization potentials from self-interaction corrected Kohn-Sham orbital energies.
abstract: We propose a simple self-interaction correction to Kohn-Sham orbital energies in order to apply ground state Kohn-Sham density functional theory to accurate predictions of core electron binding energies and chemical shifts. The proposition is explored through a series of calculations of organic compounds of different sizes and types. Comparison is made versus experiment and the "DeltaKohn-Sham" method employing separate state optimizations of the ground and core hole states, with the use of the B3LYP functional and different basis sets. A parameter alpha is introduced for a best fitting of computed and experimental ionization potentials. It is found that internal parametrizations in terms of basis set expansions can be well controlled. With a unique alpha=0.72 and basis set larger than 6-31G, the core ionization energies (IPs) of the self-interaction corrected Kohn-Sham calculations fit quite well to the experimental values. Hence, self-interaction corrected Kohn-Sham calculations seem to provide a promising tool for core IPs that combines accuracy and efficiency.
authors.affiliation: Institute of Chemical-Physical Processes, Area of Research CNR, via Moruzzi 1, 56124 Pisa, Italy.
authors.forename: Guangde
authors.initials: G
authors.lastname: Tu
authors.forename: Vincenzo
authors.initials: V
authors.lastname: Carravetta
authors.forename: Olav
authors.initials: O
authors.lastname: Vahtras
authors.forename: Hans
authors.initials: H
authors.lastname: Agren