Theoretica chimica acta

, Volume 44, Issue 2, pp 129–138

Bonded-atom fragments for describing molecular charge densities

  • F. L. Hirshfeld
Original Investigations

Abstract

For quantitative description of a molecular charge distribution it is convenient to dissect the molecule into well-defined atomic fragments. A general and natural choice is to share the charge density at each point among the several atoms in proportion to their free-atom densities at the corresponding distances from the nuclei. This prescription yields well-localized bonded-atom distributions each of which closely resembles the molecular density in its vicinity. Integration of the atomic deformation densities — bonded minus free atoms — defines net atomic charges and multipole moments which concisely summarize the molecular charge reorganization. They permit calculation of the external electrostatic potential and of the interaction energy between molecules or between parts of the same molecule. Sample results for several molecules indicate a high transferability of net atomic charges and moments.

Key words

Electron density Bonded atoms Populations Dipole moments 

Preview

Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.

References

  1. 1.
    Mulliken, R. S.: J. Chem. Phys. 3, 573 (1935); 23, 1833 (1955)Google Scholar
  2. 2.
    Kern, C. W., Karplus, M.: J. Chem. Phys. 40, 1374 (1964)Google Scholar
  3. 3.
    Politzer, P., Mulliken, R. S.: J. Chem. Phys. 55, 5135 (1971)Google Scholar
  4. 4.
    Politzer, P., Harris, R. R.: J. Am. Chem. Soc. 92, 6451 (1970)Google Scholar
  5. 5.
    Politzer, P.: Theoret. Chim. Acta (Berl.) 23, 203 (1971)Google Scholar
  6. 6.
    Politzer, P., Reggio, P. H.: J. Am. Chem. Soc. 94, 8308 (1972)Google Scholar
  7. 7.
    Politzer, P., Leung, K. C., Elliott, J. D., Peters, S. K.: Theoret. Chim. Acta (Berl.) 38, 101 (1975)Google Scholar
  8. 8.
    McLean, A. D., Yoshimine, M.: Tables of linear molecule wave functions. San José, Calif.: I.B.M. Corp. 1967Google Scholar
  9. 9.
    Coulson, C. A.: Valence, pp. 207–213. Oxford: University Press 1952Google Scholar

Copyright information

© Springer-Verlag 1977

Authors and Affiliations

  • F. L. Hirshfeld
    • 1
  1. 1.Department of Structural ChemistryWeizmann Institute of ScienceRehovothIsrael

Personalised recommendations