Decoupled Hartree‐Fock methods. II. Calculation of the potential curves of diatomic molecules

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Abstract

Applying an extended form of the Mulliken approximation and a monopole approximation for the Coulomb integrals the Hartree‐Fock nonorthogonal energy expression is decoupled. Thus, the total energy splits into a sum of one‐electron increments. The increments are minimized directly with respect to the linear coefficients and orbital exponents. Further, the ZDO approximation is used in the decoupled energy expression to avoid difficulties arising in connection with the evaluation of multicenter integrals. “Rigid core” calculations were carried out for the valence electrons of first‐row diatomics. In case of nonpolar molecules good results are obtained for equilibrium distances and force constants. The method fails for molecules with atoms having very different nuclear charges.

Original languageEnglish
Pages (from-to)569-581
Number of pages13
JournalInternational Journal of Quantum Chemistry
Volume7
Issue number3
DOIs
Publication statusPublished - 1973

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diatomic molecules
Molecules
curves
approximation
monopoles
Atoms
energy
Electrons
molecules
exponents
valence
orbitals
evaluation
coefficients
atoms
electrons

ASJC Scopus subject areas

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

Cite this

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abstract = "Applying an extended form of the Mulliken approximation and a monopole approximation for the Coulomb integrals the Hartree‐Fock nonorthogonal energy expression is decoupled. Thus, the total energy splits into a sum of one‐electron increments. The increments are minimized directly with respect to the linear coefficients and orbital exponents. Further, the ZDO approximation is used in the decoupled energy expression to avoid difficulties arising in connection with the evaluation of multicenter integrals. “Rigid core” calculations were carried out for the valence electrons of first‐row diatomics. In case of nonpolar molecules good results are obtained for equilibrium distances and force constants. The method fails for molecules with atoms having very different nuclear charges.",
author = "G. N{\'a}ray-Szab{\'o}",
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AU - Náray-Szabó, G.

PY - 1973

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AB - Applying an extended form of the Mulliken approximation and a monopole approximation for the Coulomb integrals the Hartree‐Fock nonorthogonal energy expression is decoupled. Thus, the total energy splits into a sum of one‐electron increments. The increments are minimized directly with respect to the linear coefficients and orbital exponents. Further, the ZDO approximation is used in the decoupled energy expression to avoid difficulties arising in connection with the evaluation of multicenter integrals. “Rigid core” calculations were carried out for the valence electrons of first‐row diatomics. In case of nonpolar molecules good results are obtained for equilibrium distances and force constants. The method fails for molecules with atoms having very different nuclear charges.

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