Spin‐projected EHF method. IV. Comparison of potential curves given by different one‐electron methods

Research output: Contribution to journalArticle

26 Citations (Scopus)

Abstract

Some aspects of the computer realization of the spin‐projected extended Hartree–Fock (EHF) method at the ab initio level are briefly discussed for the algorithm of solution developed in the previous papers of this series. Calculations have been performed for the BH molecule by using a small basis of contracted Gaussian lobes with the purpose of comparing the potential curves given by the different one‐electron methods RHF, UHF, UHF with subsequent spin projection, and EHF. It is concluded that the UHF and, in particular, the EHF methods give a qualitatively correct shape of the potential curve; the RHF method shows the known incorrect dissociation behavior while the potential curve obtained by subsequent spin projection of the UHF wave function exhibits spurious extrema at intermediate internuclear separations.

Original languageEnglish
Pages (from-to)29-38
Number of pages10
JournalInternational Journal of Quantum Chemistry
Volume14
Issue number1
DOIs
Publication statusPublished - 1978

Fingerprint

Wave functions
Molecules
curves
projection
range (extremes)
lobes
wave functions
dissociation
molecules

ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics
  • Condensed Matter Physics
  • Physical and Theoretical Chemistry

Cite this

@article{a0b199d1cc624968bfd4b051e6aa26cd,
title = "Spin‐projected EHF method. IV. Comparison of potential curves given by different one‐electron methods",
abstract = "Some aspects of the computer realization of the spin‐projected extended Hartree–Fock (EHF) method at the ab initio level are briefly discussed for the algorithm of solution developed in the previous papers of this series. Calculations have been performed for the BH molecule by using a small basis of contracted Gaussian lobes with the purpose of comparing the potential curves given by the different one‐electron methods RHF, UHF, UHF with subsequent spin projection, and EHF. It is concluded that the UHF and, in particular, the EHF methods give a qualitatively correct shape of the potential curve; the RHF method shows the known incorrect dissociation behavior while the potential curve obtained by subsequent spin projection of the UHF wave function exhibits spurious extrema at intermediate internuclear separations.",
author = "I. Mayer",
year = "1978",
doi = "10.1002/qua.560140104",
language = "English",
volume = "14",
pages = "29--38",
journal = "International Journal of Quantum Chemistry",
issn = "0020-7608",
publisher = "John Wiley and Sons Inc.",
number = "1",

}

TY - JOUR

T1 - Spin‐projected EHF method. IV. Comparison of potential curves given by different one‐electron methods

AU - Mayer, I.

PY - 1978

Y1 - 1978

N2 - Some aspects of the computer realization of the spin‐projected extended Hartree–Fock (EHF) method at the ab initio level are briefly discussed for the algorithm of solution developed in the previous papers of this series. Calculations have been performed for the BH molecule by using a small basis of contracted Gaussian lobes with the purpose of comparing the potential curves given by the different one‐electron methods RHF, UHF, UHF with subsequent spin projection, and EHF. It is concluded that the UHF and, in particular, the EHF methods give a qualitatively correct shape of the potential curve; the RHF method shows the known incorrect dissociation behavior while the potential curve obtained by subsequent spin projection of the UHF wave function exhibits spurious extrema at intermediate internuclear separations.

AB - Some aspects of the computer realization of the spin‐projected extended Hartree–Fock (EHF) method at the ab initio level are briefly discussed for the algorithm of solution developed in the previous papers of this series. Calculations have been performed for the BH molecule by using a small basis of contracted Gaussian lobes with the purpose of comparing the potential curves given by the different one‐electron methods RHF, UHF, UHF with subsequent spin projection, and EHF. It is concluded that the UHF and, in particular, the EHF methods give a qualitatively correct shape of the potential curve; the RHF method shows the known incorrect dissociation behavior while the potential curve obtained by subsequent spin projection of the UHF wave function exhibits spurious extrema at intermediate internuclear separations.

UR - http://www.scopus.com/inward/record.url?scp=84987112024&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84987112024&partnerID=8YFLogxK

U2 - 10.1002/qua.560140104

DO - 10.1002/qua.560140104

M3 - Article

VL - 14

SP - 29

EP - 38

JO - International Journal of Quantum Chemistry

JF - International Journal of Quantum Chemistry

SN - 0020-7608

IS - 1

ER -