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Journal of Chemical Physics / Volume 123 / Issue 10 / ARTICLES / Theoretical Methods and Algorithms

J. Chem. Phys. 123, 104104 (2005); http://dx.doi.org/10.1063/1.2033747 (6 pages)

Effect of the one-body potential on interelectronic correlation in two-electron systems

Jacob Katriel, Sudip Roy, and Michael Springborg

Physical and Theoretical Chemistry, University of Saarland, 66123 Saarbrücken, Germany

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(Received 5 July 2005; accepted 19 July 2005; published online 14 September 2005)

The correlation energies of the helium isoelectronic sequence (IS) and of Hooke’s IS are very similar and are both weakly increasing upon increasing the nuclear charge∕force constant, respectively. However, their separation into radial and angular correlations shows interesting differences. First, for intermediate (and high) values of the force constant radial correlation in Hooke’s IS is surprisingly low. Second, both systems exhibit a decrease in the relative contribution of radial versus angular correlation upon strengthening the one-body attractive potential; however, unlike the helium IS, in Hooke’s IS the radial correlation energy increases in absolute value upon strengthening the attractive one-body potential. The contribution of radial correlation to the Coulomb hole is examined and the asymptotic behavior at both strong and weak attractive potentials is considered. Radial correlation in Hooke’s IS is found to constitute about 9.3% of the total correlation energy when the spring constant approaches the limit k→∞, but 100% of the total correlation energy for k→0. Our results highlight both the similarities and the differences between the helium and Hooke’s ISs.

© 2005 American Institute of Physics

Article Outline

  1. INTRODUCTION
  2. HOOKE’S AND THE HELIUM ISOELECTRONIC SEQUENCES
    1. Hartree-Fock energies
    2. Radially correlated energies
    3. Exact energies
    4. Total and radial correlation energies
    5. The high confinement limit: Perturbation theory
    6. The low confinement limit
  3. CONTRIBUTION OF RADIAL CORRELATION TO THE COULOMB HOLE
  4. CONCLUSIONS

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KEYWORDS and PACS

Keywords

electron correlations, molecular force constants, isoelectronic series

PACS

  • 31.15.V-

    Electron correlation calculations for atoms, ions and molecules

  • 33.15.Mt

    Rotation, vibration, and vibration-rotation constants

ARTICLE DATA

Digital Object Identifier
http://dx.doi.org/10.1063/1.2033747

PUBLICATION DATA

ISSN

0021-9606 (print)  
1089-7690 (online)

Publisher

$abstract.society.value is a Member of CrossRef American Institute of Physics

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