Skip to main content
SpringerLink
Log in

Application of the independent electron pair approach to the calculation of excitation energies, ionization potentials, and electron affinities of first row atoms

  • Commentationes
  • Published:
Theoretica chimica acta Aims and scope Submit manuscript

Abstract

Excitation energies, first ionization potentials and electron affinities of first row atoms are calculated with a spin-adapted independent electron pair approximation (IEPA) combined with the direct determination of pair natural orbitals (PNOs). To enable comparison with molecular calculations Gaussian basis sets are used which are small enough to be also applicable to molecules. IEPA results for the above mentioned properties are accurate to 0.1–0.3 eV which is almost one order of magnitude better than the corresponding SCF-results. The same accuracy can be expected for molecules in which a localization of the doubly and singly occupied orbitals is possible, for instance for small hydrides. This is supported by the results of calculations on carbon hydrides.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

References

  1. Ahlrichs,R., Kutzelnigg,W.: J. Chem. Phys.48, 1819 (1968)

    Google Scholar 

  2. Jungen,M., Ahlrichs,R.: Theoret. Chim. Acta (Berl.)17, 339 (1970)

    Google Scholar 

  3. Meyer,W.: Intern. J. Quantum Chem.S5, 341 (1971)

    Google Scholar 

  4. Meyer,W.: J. Chem. Phys.58, 1017 (1973)

    Google Scholar 

  5. Meyer,W., Theoret. Chim. Acta (Berl.)35, 277 (1974)

    Google Scholar 

  6. Ahlrichs,R., Lischka,H., Staemmler,V., Kutzelnigg,W.: J. Chem. Phys.62, 1225 (1975)

    Google Scholar 

  7. Ahlrichs,R., Driessler,F., Lischka,H., Staemmler,V., Kutzelnigg,W.: J. Chem. Phys.62, 1235 (1975)

    Google Scholar 

  8. Kutzelnigg,W.: Molecular calculations including electron correlation. In: Clementi,E. (Ed.): Selected topics in molecular physics, p. 91. Weinheim: Verlag Chemie 1972

    Google Scholar 

  9. Kutzelnigg,W.: Electron correlation and electron pair theories. Topics in Current Chemistry, Vol. 41, p. 31. Berlin, Heidelberg, New York: Springer 1973

    Google Scholar 

  10. Van der Velde,G.A., Nieuwport,W.C.: Chem. Phys. Letters13, 409 (1972)

    Google Scholar 

  11. Staemmler,V., Jungen,M.: Chem. Phys. Letters16, 187 (1972)

    Google Scholar 

  12. Staemmler,V.: Theoret. Chim. Acta (Berl.)31, 49 (1973)

    Google Scholar 

  13. Staemmler,V.: Theoret. Chim. Acta (Berl.)35, 309 (1974)

    Google Scholar 

  14. Mehler,E.L.: Theoret. Chim. Acta (Berl.)35, 17 (1974)

    Google Scholar 

  15. Driessler,F., Ahlrichs,R., Staemmler,V., Kutzelnigg,W.: Theoret. Chim. Acta (Berl.)30, 315 (1973)

    Google Scholar 

  16. Staemmler,V.: Habilitationsschrift, Bochum 1975

  17. Sasaki,F., Yoshimine,M.: Phys. Rev. A9, 17, 26 (1974) and Refs. therein

    Google Scholar 

  18. Viers,J.W., Harris,F.E., Schaefer, III. H.F.: Phys. Rev. A1, 24 (1970)

    Google Scholar 

  19. Barr,T.L., Davidson,E.R.: Phys. Rev. A1, 644 (1970)

    Google Scholar 

  20. Weiss,A.W.: Phys. Rev. A3, 1 (1971)

    Google Scholar 

  21. Marchetti,M.A., Krauss,M., Weiss,A. W.: Phys. Rev. A5, 2387 (1972)

    Google Scholar 

  22. Moser,C.M., Nesbet,R.K.: Phys. Rev. A4, 1336 (1971)

    Google Scholar 

  23. Moser,C.M., Nesbet,R.K.. Phys. Rev. A6, 1710 (1972)

    Google Scholar 

  24. Davidson,E.R., Bender,C.F.: J. Chem. Phys.49, 465 (1968)

    Google Scholar 

  25. Bender,C.F., Davidson,E.R.: Chem. Phys. Letters3, 33 (1969)

    Google Scholar 

  26. Davidson,E.R., Bender,C.F.: J. Chem. Phys.56, 4334 (1972)

    Google Scholar 

  27. Nesbet,R.K.: Phys. Rev.155, 51 (1967)

    Google Scholar 

  28. Nesbet,R.K.: Phys. Rev.155, 56 (1967)

    Google Scholar 

  29. Nesbet,R.K.: Phys. Rev.175, 2 (1968)

    Google Scholar 

  30. Silverstone,H.J., Sinanoğlu,O.: J. Chem. Phys.44, 1889, 3608 (1966)

    Google Scholar 

  31. Sinanoğlu,O.: Advan. Chem. Phys.14, 237 (1969)

    Google Scholar 

  32. Jungen,M.: Theoret. Chim. Acta (Berl.)11, 193 (1968)

    Google Scholar 

  33. Huzinaga,S.: J. Chem. Phys.42, 1293 (1965)

    Google Scholar 

  34. Clementi,E.: Tables of atomic functions. IBM J. Res. Develop. Suppl. to9, 2 (1965)

    Google Scholar 

  35. Moore,C.E.: Atomic energy levels. Ntl. Bur. Std. (US), Circ. No. 467. Washington D.C.: US Government Printing Office 1949

    Google Scholar 

  36. Koopmans,T.: Physica1, 104 (1934)

    Google Scholar 

  37. Page,P.M., Goode,P.C.: Negative ions and the magnetron. London: Wiley-Interscience 1969

    Google Scholar 

  38. Celotta,R.J., Bennett,R.A., Hall,J.L.: J. Chem. Phys.60, 1740 (1974)

    Google Scholar 

  39. Herzberg,G.: Spectra of diatomic molecules. New York: Van Nostrand 1950

    Google Scholar 

  40. Gaydon,A.G.: Dissociation energies and spectra of diatomic molecules. London: Chapman and Hall 1968

    Google Scholar 

  41. Lie,G.C., Hinze,J., Liu,B.: J. Chem. Phys.59, 1872, 1887 (1973)

    Google Scholar 

  42. Frey,H.M.: J. Chem. Soc. Chem. Commun. 1024 (1972)

  43. Bender,C.F., Schaefer,III,H.F., Franceschetti,D.R., Allen,L.C.: J. Am. Chem. Soc.94, 6888 (1972)

    Google Scholar 

  44. Prophet,H.: J. Chem. Phys.38, 2345 (1963)

    Google Scholar 

  45. Herzberg,G.: Electronic spectra of polyatomic molecules. New York: Van Nostrand 1967

    Google Scholar 

  46. Herzberg,G., Johns,J.W.C.: Astrophys. J.158, 399 (1969)

    Google Scholar 

  47. Wagman,D.D., Evans,W.H, Parker,V.B., Halow,I., Bailey,S.M, Schuman,R.H.: Selected values of chemical thermodynamic properties. NBS Technical Note 270–3, 1968

  48. Green,S., Bagus,P.S., Liu,B., McLean,A.D., Yoshimine,M.: Phys. Rev. A5, 1614 (1972)

    Google Scholar 

  49. Weiss,A.W.: Phys. Rev.162, 71 (1967)

    Google Scholar 

  50. Edlen,B.: J. Chem. Phys.33, 98 (1960)

    Google Scholar 

  51. Ya'akobi,B.: Phys. Letters23, 655 (1966)

    Google Scholar 

  52. Scheer,M.D., Fine,J.: J. Chem. Phys.50, 4343 (1969)

    Google Scholar 

  53. Seman,M., Branscomb,L.M.: Phys. Rev.125, 1602 (1962)

    Google Scholar 

  54. Branscomb,L.M., Burch,D.S., Smith,S.J., Geltman,S.: Phys. Rev.111, 504 (1958)

    Google Scholar 

  55. Milstein,R., Berry,R.S.: J. Chem. Phys.55, 4146 (1971)

    Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Lehrstuhl für Theoretische Chemie, Ruhr-Universität Bochum, Germany

    Volker Staemmler

  2. Physikalisch-chemisches Institut, Universität Basel, Klingelbergstr. 80, CH-4056, Basel, Switzerland

    Martin Jungen

Authors
  1. Volker Staemmler
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Martin Jungen
    View author publications

    You can also search for this author in PubMed Google Scholar

Rights and permissions

Reprints and permissions

About this article

Cite this article

Staemmler, V., Jungen, M. Application of the independent electron pair approach to the calculation of excitation energies, ionization potentials, and electron affinities of first row atoms. Theoret. Chim. Acta 38, 303–309 (1975). https://doi.org/10.1007/BF00963469

Download citation

  • Received:

  • Issue Date:

  • DOI: https://doi.org/10.1007/BF00963469

Key words

Search

Navigation