Pseudonatural Orbitals as a Basis for the Superposition of Configurations. I. He2+
- 1 September 1966
- journal article
- research article
- Published by AIP Publishing in The Journal of Chemical Physics
- Vol. 45 (5), 1833-1839
- https://doi.org/10.1063/1.1727841
Abstract
The use of pseudonatural orbitals (PNO) is proposed to improve the rate of convergence in the superposition of configurations (SOC). Natural orbitals are determined for selected electron pairs in the Hartree—Fock field of the n−2 electron core and are then used as the basis for the total SOC calculation. Since these natural orbitals are not natural for the n‐electron system they are considered false or pseudonatural orbitals when used in the n‐electron problem. The PNO basis has been applied to He2+ and H3 to test the convergence. Complete results are reported here only for He2+. The PNO's are quite successful in speeding up the convergence of the SOC and rendering the calculation of correlation energy quite practical in general. Gaussian‐type orbitals (GTO) are used throughout and were not a serious impediment to obtaining quantitative accuracy. In fact the large number of unoccupied Hartree—Fock orbitals consequent upon the use of a GTO basis permit a straightforward determination of the PNO orbitals.Keywords
This publication has 20 references indexed in Scilit:
- The Quantum Theory of ValenceAnnual Review of Physical Chemistry, 1965
- Configuration-Interaction Calculation of H3 and H2The Journal of Chemical Physics, 1965
- Direct Determination of Natural Orbitals and Natural Expansion Coefficients of Many-Electron Wavefunctions. I. Natural Orbitals in the Geminal Product ApproximationThe Journal of Chemical Physics, 1964
- Localized Atomic and Molecular OrbitalsReviews of Modern Physics, 1963
- On the Calculations of Real Wave Functions In Natural Form for Two-Electron SystemsReviews of Modern Physics, 1963
- Brueckner's Theory and the Method of Superposition of ConfigurationsPhysical Review B, 1958
- Correlation Problem in Many‐Electron Quantum Mechanics I. Review of Different Approaches and Discussion of Some Current IdeasAdvances in Chemical Physics, 1958
- Natural Orbitals in the Quantum Theory of Two-Electron SystemsPhysical Review B, 1956
- The molecular orbital theory of chemical valency XVI. A theory of paired-electrons in polyatomic moleculesProceedings of the Royal Society of London. Series A - Mathematical and Physical Sciences, 1953
- Über den Grundzustand des HeliumatomsThe European Physical Journal A, 1928