Theoretica chimica acta

, Volume 52, Issue 1, pp 55–66 | Cite as

Possible artifacts occurring in the calculation of intermolecular energies from delocalized pictures

  • J. P. Malrieu
  • F. Spiegelmann
Original Investigations

Abstract

The intermolecular energy between two identical subsystems may be calculated from symmetrydelocalized MO's resulting for instance from a preliminary SCF calculation of the supersystem. Then each second-order energy correction mixes intramolecular correlation,R−6 intermolecular dispersion energy, andR−3 components. TheR−3 components disappear through subtle cancellations. The shifted Epstein-Nesbet energy denominators introduce an artificial second-order intermolecularR−1 component, which would be cancelled by off-diagonal third-order terms, as well as a bad asymptotic limit at infinite distances. TheR−1 artifact will also occur in strong symmetrical chemical bonds calculated in the Epstein-Nesbet perturbation scheme from delocalized MO's. These defects will occur in all variational approximate CI techniques which neglect off-diagonal elements between delocalized doubly excited determinants. These artifacts are avoided when using the Moller-Plesset definition of the zeroth order Hamiltonian or when starting from (SCF)localized MO's (even in the Epstein-Nesbet perturbation). The discussion is exemplified on an accurateab initio calculation of the Ar2 molecule.

Key words

Delocalized MOs 

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Copyright information

© Springer-Verlag 1979

Authors and Affiliations

  • J. P. Malrieu
    • 1
  • F. Spiegelmann
    • 1
  1. 1.Laboratoire de Physique QuantiqueUniversité Paul SabatierToulouse CedexFrance

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