Vitale V, Della Sala F, Görling A (2005)
Publication Type: Journal article, Original article
Publication year: 2005
Original Authors: Vitale V., Della Sala F., Görling A.
Publisher: American Institute of Physics (AIP)
Book Volume: 122
Article Number: 244102
Journal Issue: 24
DOI: 10.1063/1.1938868
An effective exact-exchange Kohn-Sham approach for the treatment of excited electronic states, the generalized adiabatic connection open-shell localized Hartree-Fock (GAC-OSLHF) method is presented. The GAC-OSLHF method is based on the generalized adiabatic connection Kohn-Sham formalism and therefore capable of treating excited electronic states, which are not the energetically lowest of their symmetry. The method is self-interaction free and allows for a fully self-consistent computation of excited valence as well as Rydberg states. Results for atoms and small- and medium-size molecules are presented and compared to restricted open-shell Hartree-Fock (ROHF) and time-dependent density-functional results as well as to experimental data. While GAC-OSLHF and ROHF results are quite close to each other, the GAC-OSLHF method shows a much better convergence behavior. Moreover, the GAC-OSLHF method as a Kohn-Sham method, in contrast to the ROHF approach, represents a framework which allows also for a treatment of correlation besides an exchange by appropriate functionals. In contrast to the common time-dependent density-functional methods, the GAC-OSLHF approach is capable of treating doubly or multiply excited states and can be easily applied to molecules with an open-shell ground state. On the nodal planes of the energetically highest occupied orbital, the local multiplicative GAC-OSLHF exchange potential asymptotically approaches a different, i.e., nonzero, value than in other regions, an asymptotic behavior which is known from exact Kohn-Sham exchange potentials of ground states of molecules. © 2005 American Institute of Physics.
APA:
Vitale, V., Della Sala, F., & Görling, A. (2005). Open-shell localized Hartree-Fock method based on the generalized adiabatic connection Kohn-Sham formalism for a self-consistent treatment of excited states. Journal of Chemical Physics, 122(24). https://doi.org/10.1063/1.1938868
MLA:
Vitale, V., Fabio Della Sala, and Andreas Görling. "Open-shell localized Hartree-Fock method based on the generalized adiabatic connection Kohn-Sham formalism for a self-consistent treatment of excited states." Journal of Chemical Physics 122.24 (2005).
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