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Self-consistent field with pseudowavefunctions

Journal Article · · J. Chem. Phys., v. 64, no. 2, pp. 492-499
DOI:https://doi.org/10.1063/1.432211· OSTI ID:4081707

A computational method is given in which the energy of an atom is computed by using pseudowavefunctions only. The method centers on a model energy expression E/sub M/ which is similar to the Hartree--Fock energy expression, but contains only pseudowavefunctions. A theorem is proved according to which the Hartree--Fock orbitals can be transformed by a linear transformation into a set of uniquely defined pseudowavefunctions which have the property that, when substituted into E/sub M/, this quantity will closely approximate the Hartree-- Fock energy E/sub F/. The new method is then formulated by identifying the total energy of an atom with the minimum of E/sub M/. Application of the energy minimum principle leads to a set of equations for the pseudowavefunctions which are similar to but simpler than the Hartree--Fock equations. These equations contain pseudopotentials for which explicit expressions are derived. The possibility of replacing these pseudopotentials by simpler model potentials is discussed, and the criteria for the selection of the model potential are outlined. (AIP)

Research Organization:
Department of Physics, Fordham University, New York, New York 10458
Sponsoring Organization:
USDOE
NSA Number:
NSA-33-021234
OSTI ID:
4081707
Journal Information:
J. Chem. Phys., v. 64, no. 2, pp. 492-499, Journal Name: J. Chem. Phys., v. 64, no. 2, pp. 492-499; ISSN JCPSA
Country of Publication:
United States
Language:
English

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