Core ionization potentials from self-interaction corrected Kohn-Sham Orbital energies
2007 (English)In: Journal of Chemical Physics, ISSN 0021-9606, E-ISSN 1089-7690, Vol. 127, no 17, 174110- p.Article in journal (Refereed) Published
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 " ΔKohn -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 α 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 α=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.
Place, publisher, year, edition, pages
2007. Vol. 127, no 17, 174110- p.
Binding energy, Chemical shift, Density functional theory, Electrons, Organic compounds
IdentifiersURN: urn:nbn:se:kth:diva-8409DOI: 10.1063/1.2777141ISI: 000250787300012ScopusID: 2-s2.0-35948963605OAI: oai:DiVA.org:kth-8409DiVA: diva2:13721
QC 20100906. Previous title: Self-interaction correction to Kohn-Sham core orbital energies in molecules.2008-05-092008-05-092011-08-30Bibliographically approved