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Dissection of Basis Set Superposition Error at SCF and Correlated Levels. HF Dimer.
Chemistry and Biochemistry Faculty Publications (1989)
  • Zdzisław Latajka
  • Steve Scheiner, Utah State University
Abstract

Orbitals normally assigned to H or F atoms within the context of the 6-31G∗ or 6-31G∗∗ basis sets are centered at several different positions in the vicinity of a HF molecule and the basis-set superposition error (BSSE) calculated as the energy lowering engendered in HF. For ghost orbitals of either H or F type, the outer valence shell is responsible for the bulk of the total BSSE at either the SCF or MP2 level. The contribution of polarization functions is highly sensitive to the value chosen for the orbital exponent; the BSSE varies from nearly negligible for large exponents (the typical result of energy-based optimization) to values larger than the valence-shell contribution for more diffuse functions. Similar observations apply to perturbations of the monomer dipole moment which give rise to one element of secondary BSSE.

Keywords
  • dissection,
  • basis,
  • set,
  • superposition,
  • error,
  • SCF,
  • levels
Disciplines
Publication Date
January 1, 1989
Citation Information
Dissection of Basis Set Superposition Error at SCF and Correlated Levels. HF Dimer Z. Latajka and S. Scheiner J. Mol. Struct., Theochem, 1989 199, 9-22.