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Journal of Chemical Physics / Volume 115 / Issue 4 / ARTICLES / Theoretical Methods and Algorithms

J. Chem. Phys. 115, 1626 (2001); doi:10.1063/1.1383585 (9 pages)

Impact of electron–electron cusp on configuration interaction energies

David Prendergast1, M. Nolan2, Claudia Filippi1, Stephen Fahy1, and J. C. Greer2

1Department of Physics, University College, Cork, Ireland
2NMRC, University College, Cork, Ireland

(Received 7 March 2001; accepted 15 May 2001)

The effect of the electron–electron cusp on the convergence of configuration interaction (CI) wave functions is examined. By analogy with the pseudopotential approach for electron–ion interactions, an effective electron–electron interaction is developed which closely reproduces the scattering of the Coulomb interaction but is smooth and finite at zero electron–electron separation. The exact many-electron wave function for this smooth effective interaction has no cusp at zero electron–electron separation. We perform CI and quantum Monte Carlo calculations for He and Be atoms, both with the Coulomb electron–electron interaction and with the smooth effective electron–electron interaction. We find that convergence of the CI expansion of the wave function for the smooth electron–electron interaction is not significantly improved compared with that for the divergent Coulomb interaction for energy differences on the order of 1 mHartree. This shows that, contrary to popular belief, description of the electron–electron cusp is not a limiting factor, to within chemical accuracy, for CI calculations. © 2001 American Institute of Physics.

© 2001 American Institute of Physics

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KEYWORDS and PACS

Keywords

helium neutral atoms, beryllium, configuration interactions, Monte Carlo methods

PACS

  • 31.15.V-

    Electron correlation calculations for atoms, ions and molecules

ARTICLE DATA

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http://link.aip.org/link/doi/10.1063/1.1383585

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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