Theoretica chimica acta

, Volume 28, Issue 3, pp 213–222 | Cite as

The influence of polarization functions on molecular orbital hydrogenation energies

  • P. C. Hariharan
  • J. A. Pople


Polarization functions are added in two steps to a split-valence extended gaussian basis set: d-type gaussians on the first row atoms C. N, O and F and p-type gaussians on hydrogen. The same d-exponent of 0.8 is found to be satisfactory for these four atoms and the hydrogen p-exponent of 1.1 is adequate in their hydrides. The energy lowering due to d functions is found to depend on the local symmetry around the heavy atom. For the particular basis used, the energy lowerings due to d functions for various environments around the heavy atom are tabulated. These bases are then applied to a set of molecules containing up to two heavy atoms to obtain their LCAO-MO-SCF energies. The mean absolute deviation between theory and experiment (where available) for heats of hydrogenation of closed shell species with two non-hydrogen atoms is 4 kcal/mole for the basis set with full polarization. Estimates of hydrogenation energy errors at the Hartree-Fock limit, based on available calculations, are given.


Hydride Heavy Atom Polarization Function Local Symmetry Closed Shell 
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Polarisationsfunktionen werden in zwei Schritten einer Basis von Gauß-Orbitalen hinzugefügt: d-Gauß-Funktionen für die Atome C, N, O und F und p-Gaußfunktionen für H. In allen Fällen ist ein d-Exponent von 0.8 bzw. ein p-Exponent von 1.1 bei den Hydriden befriedigend. Dabei hängt die Energieerniedrigung, die tabelliert wiedergegeben wird, von der lokalen Symmetrie am schweren Kern ab. Mit dieser Basis wird dann die LCAO-MO-SCF-Energie für Moleküle mit 2 schweren Atomen berechnet. Die mittlere absolute Abweichung zwischen Theorie und Experiment für Hydrierungswärmen von solchen Molekülen (mit abgeschlossener Schale) ist 4 kcal/Mol bei Einschluß aller Polarisationsfunktionen. Der Schätzwert für Hydrierungswärmen in der Hartree-Fock-Grenze wird ebenfalls angegeben.


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Copyright information

© Springer-Verlag 1973

Authors and Affiliations

  • P. C. Hariharan
    • 1
  • J. A. Pople
    • 1
  1. 1.Department of ChemistryCarnegie-Mellon UniversityPittsburgh

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