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Theoretica chimica acta

, Volume 35, Issue 1, pp 17–32 | Cite as

Orbital correlation effects: The independent pair-potential approximation with application to the ground state and first ionized state of boron hydride

  • E. L. Mehler
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Abstract

A new method is proposed for calculating correlation effects in atomic and molecular systems. The basis of the method is the formulation of a set of partial configuration expansions which yield directly variational orbital correlation corrections which are appropriately summed in order to obtain an estimate of the total correlation energy. This method is applied to the ground state of boron hydride and its cation at the equilibrium distance of BH. The results of the method are compared in detail with independent electron pair results and second order CI results. It is further shown that multiple substitutions are approximately accounted for in this method and the extent to which they are included is compared with other approximations. Finally, three methods of increasing accuracy, aimed at reducing the necessary computational effort, are given for determining the vertical ionization potential. The most economical method yields an IP of 9.70 eV or 0.03 eV less than the experimental IP. Completion of the basis is estimated to improve this value to 9.77 eV.

Key words

Boron hydride Correlation energy Ionization potential Orbital correlation 

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Copyright information

© Springer-Verlag 1974

Authors and Affiliations

  • E. L. Mehler
    • 1
    • 2
  1. 1.Laboratory of Structural ChemistryUniversity of GroningenGroningenThe Netherlands
  2. 2.BiozentrumUniversität BaselBaselSwitzerland

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