Theoretica chimica acta

, Volume 43, Issue 1, pp 1–27 | Cite as

Analysis of the chemical bond

I. The binding energy of the MO-LCAO scheme with an approximate correction for left-right correlation, and its physical fragmentation
  • Frank Driessler
  • Werner Kutzelnigg
Original Investigations

Abstract

The energy expression of the MO-LCAO scheme is corrected approximately for the left-right correlation such that it leads to the correct dissociation limit. Together with the correlation correction a correction is applied to the interference term, whereas the sharing penetration effects are neglected. The derivation of this corrected approximate energy formula is suggested from an analysis of binding in H2+ and H2. The binding energy consists mainly of three contributions: interference, quasiclassical interaction, promotion. Two-electron interference contributions are absorbed into the one-electron terms. The basis dependence of the fragmentation of the binding energy is discussed and an appropriate hybrid basis is constructed. Rotational invariance is found to a high degree of accuracy. In terms of the proposed scheme the binding in several diatomic and polyatomic molecules is analysed. The individual contributions to the binding energy turn out to be physically meaningful.

Key words

Chemical bond Analysis of binding energy Interference Promotion state Left-right correlation 

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Copyright information

© Springer-Verlag 1976

Authors and Affiliations

  • Frank Driessler
    • 1
  • Werner Kutzelnigg
    • 1
  1. 1.Lehrstuhl für Theoretische ChemieRuhr-UniversitätBochumGermany

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