Theoretica chimica acta

, Volume 40, Issue 1, pp 47–60 | Cite as

An ab initio study of the effect of the 3d orbitals of phosphorus on the properties of the phosphate group

  • David Perahia
  • Alberte Pullman
  • Hélène Berthod
Commentationes

Abstract

A large number of properties of the dimethylphosphate anion (DMP), model system for the phosphate group of the nucleic acids and the phospholipid components of membranes, has been investigated by the SCF ab initio procedure including the 3d orbitals of the phosphorus atom in the gaussian basis set and the results of the computations were compared with similar results obtained previously without taking these orbitals into account. The properties investigated include the conformational states of DMP with respect to the torsion about the P-Oester bonds, the distribution of the electronic charges, the molecular electrostatic potentials generated by DMP, the characteristics of the molecular orbitals, particularly the electronic isodensity maps, the hydration scheme. Qualitatively, the introduction of the 3d orbitals modifies little the general aspects of the results obtained for most of the properties studied. On the quantitative level significant, although generally not great, modifications may be noticed with respect to some features of these properties. One of the strongest influences of the introduction of the 3d orbitals concerns the decrease of the net electronic charges in DMP.

Key words

Dimethylphosphate Nucleic acids Phospholipids 

Preview

Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.

References

  1. 1.
    Perahia,D., Pullman,B., Saran,A.: C.R. Acad. Sci. Paris 277, Série D, 2257 (1973)Google Scholar
  2. 2.
    Perahia,D., Pullman,B., Saran,A.: Biochim. Biophys. Acta 340, 299 (1974)Google Scholar
  3. 3.
    Berthod,H., Pullman,A.: Chem. Phys. Letters 32, 233 (1975)Google Scholar
  4. 4.
    Pullman,A., Berthod,H., Gresh,N.: Chem. Phys. Letters 33, 11 (1975)Google Scholar
  5. 5.
    Pullman,B., Pullman,A., Berthod,H., Gresh,N.: Theoret. Chim. Acta, (Berl.) in pressGoogle Scholar
  6. 6.
    David,D.J.: IBMOL IBM 370 Version, Centre de Calcul de l'E.N.S.J.F. Paris (1969)Google Scholar
  7. 7.
    Clementi,E., Davis,D.R.: J. Comput. Phys. 1, 223 (1966)Google Scholar
  8. 8.
    Clementi,E., Veillard,A.: IBMOL version II for the IBM 7094 IBM Technical Report, San Jose (1966)Google Scholar
  9. 9.
    Hehre,W.G., Stewart,R.F., Pople,J.A.: J. Chem. Phys. 51, 2657 (1969)Google Scholar
  10. 10.
    Hehre,W.G., Ditchfield,R., Stewart,R.F., Pople,J.A.: J. Chem. Phys. 52, 2769 (1970)Google Scholar
  11. 11.
    Hehre,W.G., Lathan,W.A., Ditchfield,R., Newton,M.D., Pople,J.A.: Q.C.P.E. Program No 236Google Scholar
  12. 12.
    Keeton,M. and Santry,D.P.: Chem. Phys. Letters 7, 105 (1970)Google Scholar
  13. 13.
    Huzinaga,S.: J. Chem. Phys. 42, 1293 (1965)Google Scholar
  14. 14.
    Bonaccorsi,R., Scrocco,E., Tomasi,J.: J. Chem. Phys. 52, 5270 (1970)Google Scholar
  15. 15.
    Bonaccorsi,R., Scrocco,E., Tomasi,J.: Private communicationGoogle Scholar
  16. 16.
    Newton,M.D.: J. Am. Chem. Soc. 95, 256 (1973)Google Scholar
  17. 17.
    Lakshminarayanan,A.V., Sasisekharan,V.: Biopolymers 8, 489 (1969)Google Scholar
  18. 18.
    Olson,W.K., Flory,P.J.: Biopolymers 11, 25 (1972)Google Scholar
  19. 19.
    Yathindra,N., Sundralingam,M.: Proc. Natl. Acad. Sc. US 71, 3325 (1974)Google Scholar
  20. 20.
    Mulliken,R.S.: J. Chem. Phys. 23, 1833 (1955)Google Scholar
  21. 21.
    Guest,M.F., Hillier,I.H., Saunders,V.R.: J. Chem. Soc. Faraday Transactions 5, 867 (1972)Google Scholar
  22. 22.
    Hillier,I.H., Saunders,V.R.: J. Chem. Soc. A, 2475 (1970)Google Scholar
  23. 23.
    Boyd,D.B.: Theoret. Chim. Acta (Berl.) 18, 184 (1970)Google Scholar
  24. 24.
    Boyd,D.B., Lipscomb,W.N.: J. Chem. Phys. 46, 910 (1967)Google Scholar
  25. 25.
    Demuyinck,J., Veillard,A.: Chem. Commun. 873 (1970)Google Scholar
  26. 26.
    Johansen,H.: Theoret. Chim. Acta (Berl.) 32, 273 (1974)Google Scholar
  27. 27.
    McAloon,B.J., Perkins,P.G.: Theoret. Chim. Acta (Berl.) 24, 102 (1972)Google Scholar
  28. 28.
    Alving,R.E., Laki,K.: J. Theoret. Biol. 34, 199 (1972)Google Scholar
  29. 29.
    Boyd,D.B., Lipscomb,W.N.: J. Theoret. Biol. 25, 403 (1969)Google Scholar
  30. 30.
    See for instance Armbruster,A.M., Pullman,A.: Intern. J. Quantum Chem. S8, 169 (1974)Google Scholar

Copyright information

© Springer-Verlag 1975

Authors and Affiliations

  • David Perahia
    • 1
  • Alberte Pullman
    • 1
  • Hélène Berthod
    • 1
  1. 1.Institut de Biologie Physico-ChimiqueLaboratoire de Biochimie Théorique associé au C.N.R.S.Paris

Personalised recommendations