Analysis of the quality of Kohn-Sham orbitals for subsequent MRSD-CI calculations of excitation energies
Hupp T, Engels B, Della Sala F, Görling A (2003)
Publication Type: Journal article, Original article
Publication year: 2003
Journal
Original Authors: Hupp T., Engels B., Della Sala F., Görling A.
Publisher: Oldenbourg Verlag
Book Volume: 217
Pages Range: 133-159
Journal Issue: 2
URI: https://www.scopus.com/record/display.uri?eid=2-s2.0-0037283150&origin=inward
Abstract
In the present work we study the properties of Kohn-Sham orbitals used in subsequent CI methods for the computation of electronic excitation energies in terms of orbital relaxation, static and dynamical correlation effects. As model systems, we use the water and the ethene molecule. As sets of orbitals, we use orbitals from an effective exact exchange Kohn-Sham method, the localized Hartree-Fock (LHF) method, as well as BLYP and HF orbitals. Our study shows that the use of LHF orbitals leads to negligible static correlation effects and thus facilitates assignments of excitation spectra, but it also shows that the remaining correlation contributions have to be taken into account carefully since error cancellation is only found in some fortitious cases. The comparison of LHF and BLYP orbitals shows that the BLYP orbitals are less suited for the description of the cationic system and as a consequence for the computation of Rydberg states.
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APA:
Hupp, T., Engels, B., Della Sala, F., & Görling, A. (2003). Analysis of the quality of Kohn-Sham orbitals for subsequent MRSD-CI calculations of excitation energies. Zeitschrift für Physikalische Chemie-International Journal of Research in Physical Chemistry & Chemical Physics, 217(2), 133-159.
MLA:
Hupp, T., et al. "Analysis of the quality of Kohn-Sham orbitals for subsequent MRSD-CI calculations of excitation energies." Zeitschrift für Physikalische Chemie-International Journal of Research in Physical Chemistry & Chemical Physics 217.2 (2003): 133-159.
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