Abstract
The wavefunctions and various partitions of the energy are examined for a variety of small molecules (H2, H3, H4, HeH, HeH2, He2, LiH, and BH) in order to isolate the factors crucial for bond formation. We find that a natural partition of the energy leads to the conclusion that the crucial factor is the exchange, or nonclassical, part of the kinetic energy, T x. The change in T xupon pushing the atoms towards one another is the dominant term in the binding energy; it is negative when the resulting molecule is stable and positive when it is unstable. We show that T x is related to the interference kinetic energy considered by Ruedenberg.
Zusammenfassung
Die Wellenfunktionen und verschiedene Zerlegungen der Energie werden für eine Reihe kleiner Moleküle untersucht (H2, H3, H4, HeH, HeH2, He2, LiH und BH), um die Faktoren zu finden, die für die Bindungsbildung ausschlaggebend sind. Die natürliche Zerlegung der Energie läßt die Folgerung zu, daß der bestimmende Faktor der Austauschanteil T x(oder nichtklassische Anteil) der kinetischen Energie ist. Die Änderung von T xbeim Zusammenführen der Atome ist der dominierende Term für die Bindungsenergie; er ist negativ, wenn das resultierende Molekül stabil ist, und positiv, falls es instabil ist. Es wird gezeigt, daß T x im Zusammenhang zum Wechselwirkungsanteil der kinetischen Energie nach Ruedenberg steht.
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Partially supported by a grant (GP-15423) from the National Science Foundation. This paper is based on a portion of the PhD thesis (California Institute of Technology, 1970) by CWW.
National Science Foundation Predoctoral Trainee.
Alfred P. Sloan Foundation Research Fellow.
Contribution No. 3917.
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Wilson, C.W., Goddard, W.A. The role of kinetic energy in chemical binding. Theoret. Chim. Acta 26, 195–210 (1972). https://doi.org/10.1007/BF00529306
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DOI: https://doi.org/10.1007/BF00529306