The Hartree product and the description of local and global quantities in atomic systems: A study within Kohn-Sham theory
- Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, P.O. Box 999, Richland, Washington 99352 (United States)
The Hartree product is analyzed in the context of Kohn-Sham theory. The differential equations that emerge from this theory are solved with the optimized effective potential using the Krieger, Li, and Iafrate approximation, in order to get a local potential as required by the ordinary Kohn-Sham procedure. Because the diagonal terms of the exact exchange energy are included in Hartree theory, it is self-interaction free and the exchange potential has the proper asymptotic behavior. We have examined the impact of this correct asymptotic behavior on local and global properties using this simple model to approximate the exchange energy. Local quantities, such as the exchange potential and the average local electrostatic potential are used to examine whether the shell structure in an atom is revealed by this theory. Global quantities, such as the highest occupied orbital energy (related to the ionization potential) and the exchange energy are also calculated. These quantities are contrasted with those obtained from calculations with the local density approximation, the generalized gradient approximation, and the self-interaction correction approach proposed by Perdew and Zunger. We conclude that the main characteristics in an atomic system are preserved with the Hartree theory. In particular, the behavior of the exchange potential obtained in this theory is similar to those obtained within other Kohn-Sham approximations. (c) 2000 American Institute of Physics.
- OSTI ID:
- 20215051
- Journal Information:
- Journal of Chemical Physics, Vol. 112, Issue 3; Other Information: PBD: 15 Jan 2000; ISSN 0021-9606
- Country of Publication:
- United States
- Language:
- English
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