Theoretica chimica acta

, Volume 54, Issue 1, pp 83–91 | Cite as

On the contribution of higher-order excitations to correlation energies: The ground state of the water molecule

  • Stephen Wilson
  • David M. Silver
Original Investigations

Abstract

Using the results of a configuration interaction calculation reported by Rosenberg and Shavitt, we derive an approximation to the correlation energy which may be associated with the sum to infinite order of all linked diagrams involving singly- and doubly-excited states. This result is compared with that obtained by calculation of the energy through third-order. The fourth-order linked diagrams involving quadruply-excited states are computed. It is shown that there is a considerable degree of cancellation between the fourth-order linked diagram energy terms involving doubly-excited intermediate states only and those which contain quadruply-excited states.

Key words

Higher-order excitations, contribution of ∼ to correlation energies Water molecule 

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Copyright information

© Springer-Verlag 1979

Authors and Affiliations

  • Stephen Wilson
    • 1
  • David M. Silver
    • 2
  1. 1.Science Research CouncilDaresbury LaboratoryDaresburyEngland
  2. 2.Applied Physics LaboratoryThe Johns Hopkins UniversityLaurelUSA

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