Skip to main content
SpringerLink
Log in

Open shell cndo treatments on small and aliphatic radicals. Electronic spectra and some ground state properties

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

Abstract

Electronic spectra, ionization potentials and ground state geometries of nine radicals containing 3 or 4 atoms were studied by configuration interaction treatment based on SCF MO's (standard CNDO/2 and the version of Del Bene and Jaffé). SCF open shell procedures used were those developed by Roothaan and Longuet-Higgins, Pople (LHP). It appears that the LHP procedure is satisfactory; if based on the SCF MO's of Del Bene and Jaffé it gives results which agree fairly well with observed electronic spectra and first ionization potentials.

Zusammenfassung

Elektronenspektren, Ionisierungspotentiale und Grundzustandsgeometrien von neun drei und vieratomigen Radikalen wurden mit Hilfe der Konfigurationswechselwirkungsmethode mit SCF MO (CNDO/2 und Version nach Del Bene and Jaffé) untersucht. Es wurden die SCF “open-shell”-Verfahren nach Roothaan, Longuet-Higgins und Pople (LHP) benutzt. Es scheint daß das LHP-Verfahren zu zufriedenstellenden Ergebnissen führt; zusammen mit SCF-MO nach Del Bene und Jaffé ergibt sich bei Elektronenspektren und Ionisierungspotentialen befriedigende Übereinstimmung mit dem Experiment.

Résumé

On a étudié les spectres électroniques, les potentiels d'ionisation et la géometrie de l'état fondamental de 9 radicaux contenant 3 ou 4 atomes par la méthode de l'interaction des configurations fondée sur les orbites moléculaires autocohérentes (standard CNDO/2 et la version de Del Bene et Jaffé). Les procédés autocohérents pour les couches ouvertes utilisés étaient ceux de Roothaan et de Longuet-Higgins, Pople (LHP). On voit que le procédé LHP est satisfaisant; dans le cas où il est basé sur les MO autocohérents de Del Bene et Jaffé, il donne des résultats qui sont en assez bon accord avec les spectres électroniques et les premiers potentiels d'ionisation observés.

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. For references see Zahradník,R., Čársky, P.: In: Progr. physic. org. Chem. (A.Streitwieser, Jr., R.W.Taft), submitted for publication.

  2. Kikuchi, O.: Bull. chem. Soc. Japan 42, 47 (1969).

    Google Scholar 

  3. Pople, J.A., Segal, G.A.: J. chem. Physics 44, 3289 (1966).

    Google Scholar 

  4. Andrews, P.R.: J. molecular Structure 6, 85 (1970).

    Google Scholar 

  5. Grimm, F.A., Godoy, J.: Chem. Physics Letters 6, 336 (1970).

    Google Scholar 

  6. Underwood, G.R., Vogel, V.L.: Molecular Physics 19, 621 (1970).

    Google Scholar 

  7. Benson, H.G., Bowles, A.J., Hudson, A., Jackson, R.A.: Molecular Physics 20, 713 (1971).

    Google Scholar 

  8. Wood, D.E., Lloyd, R.V., Lathan, W.A.: J. Amer. chem. Soc. 93, 4145 (1971).

    Google Scholar 

  9. Beveridge, D.L., Guth, E.: J. chem. Physics 55, 458 (1971).

    Google Scholar 

  10. Kelkar, V.K., Balla, K.C., Khubchandani, P.G.: J. molecular Structure 9, 383 (1971).

    Google Scholar 

  11. Boyd, R.J., Whitehead, M.A.: J. C. S. Dalton 1972, 78.

  12. Boyd,R.J., Whitehead,M.A.: J. C. S. Dalton 1972, 81.

  13. Cornford, A.B, Frost, D.C, Herring, F.G., McDowell, C.A.: J. chem. Physics 54, 1872 (1971).

    Google Scholar 

  14. Cornford, A.B., Frost, D.C., Herring, F.G., McDowell, C.A.: Chem. Physics Letters 10, 345 (1971).

    Google Scholar 

  15. Boyd, R.J., Whitehead, M.A.: J. chem. Soc. (A) Inorg. Phys. Theor. 1971, 3579.

  16. King, G.W., Santry, D.P., Warren, C.H.: J. chem. Physics50, 4565 (1969).

    Google Scholar 

  17. Baird, N.C., Dewar, M.J.S.: J. chem. Physics 50, 1262 (1969).

    Google Scholar 

  18. Dewar, M.J.S., Haselbach, E.: J. Amer. chem. Soc. 92, 590 (1970).

    Google Scholar 

  19. Haselbach, E.: Chem. Physics Letters 7, 428 (1970).

    Google Scholar 

  20. Kollmar, H.: Chem. Physics Letters 8, 533 (1971).

    Google Scholar 

  21. Nixon, R.N.: Molecular Physics 12, 83 (1967).

    Google Scholar 

  22. Kroto, H.W., Santry, D.P.: J. chem. Physics 47, 2736 (1967).

    Google Scholar 

  23. Kirby, G.H., Miller, K.: Chem. Physics Letters 3, 643 (1969).

    Google Scholar 

  24. Hoffmann, R., Swaminathan, S., Odell, B.G., Gleiter, R.: J. Amer. chem. Soc. 92, 7091 (1970).

    Google Scholar 

  25. Roothaan, C.C. J.: Rev. mod. Physics 32, 179 (1960).

    Google Scholar 

  26. Longuet-Higgins, H.C., Pople, J.A.: Proc. physic. Soc. 68A, 591 (1955).

    Google Scholar 

  27. Pople, J.A., Segal, G.A.: J. chem. Physics 43, S136 (1965).

    Google Scholar 

  28. Del Bene, J., Jaffé, H.H.: J. chem. Physics 48, 1807 (1968).

    Google Scholar 

  29. Pople, J.A., Beveridge, D.L., Dobosh, P.A.: J. chem. Physics 47, 2026 (1967).

    Google Scholar 

  30. Bodor, N., Dewar, M.J.S., Harget, A., Haselbach, E.: J. Amer. chem. Soc. 92, 3854 (1970).

    Google Scholar 

  31. Herzberg, G.: Molecular spectra and molecular structure. III. Electronic spectra and electronic structure of polyatomic molecules. New York: Nostrand Reinhold Comp. 1966.

    Google Scholar 

  32. Atkins, P.W., Symons, M.C.R.: The structure of inorganic radicals. Amsterdam: Elsevier Publ. Comp. 1967.

    Google Scholar 

  33. Adams, O.W, Lykos, P,G.: J. chem. Physics 34, 1444 (1961).

    Google Scholar 

  34. Hush, N.S., Pople, J.A.: Trans. Faraday Soc. 51, 600 (1955).

    Google Scholar 

  35. Zahradník, R., Čársky, P.: J. physic. Chem. 74, 1235 (1970).

    Google Scholar 

  36. Giessner-Prettre, C., Pullman, A.: Theoret. chim. Acta (Berl.) 13, 265 (1969).

    Google Scholar 

  37. Brundle, C.R., Neumann, D., Price, W.C., Evans, D., Potts, A.W., Streets, D.G.: J. chem. Physics 53, 705 (1970).

    Google Scholar 

  38. Lifshitz, C., Hughes, B.M., Tiernan, T.O.: Chem. Physics Letters 7, 469 (1970).

    Google Scholar 

  39. McClellan, A.L.: Tables of experimental dipole moments. San Francisco and London: W.H. Freeman and Comp. 1963.

    Google Scholar 

  40. Salahub, D.R., Sandorfy, C.: Theoret. chim. Acta (Berl.) 20, 227 (1971).

    Google Scholar 

  41. Gordon, M.S., Pople, J.A.: J. chem. Physics 49, 4643 (1968).

    Google Scholar 

  42. Ogilvie, J.S.: Spectrochim. Acta 23A, 737 (1967).

    Google Scholar 

  43. Claxton, T.A.: Trans. Faraday Soc. 67, 897 (1971).

    Google Scholar 

  44. Walsh,A.D.: J. chem. Soc. 1953, 2266 and the following papers.

  45. Mathews, C.W., Innes, K.K.: J. molecular Spectr. 15, 199 (1965).

    Google Scholar 

  46. Mathews, C.W., Innes, K.K.: J. molecular Spectr. 19, 203 (1966).

    Google Scholar 

  47. Forrester, A.R., Hay, J.M., Thompson, R.H.: Organic chemistry of stable free radicals. London: Academic Press 1968.

    Google Scholar 

  48. Salotto, A.W., Burnelle, L.: J. chem. Physics 53, 333 (1970).

    Google Scholar 

  49. Kamachi, M., Kuwata, K., Murahashi, S.: J. physic. Chem. 75, 164 (1971).

    Google Scholar 

  50. Brivati, J.A., Root, K.D.J., Symons, M.C.R, Tinling, D.J.A.: J. chem. Soc. (A) 1969, 1942.

  51. Čársky, P., Zahradník, R.: Collect. czechoslov. chem. Commun. 36, 961 (1971).

    Google Scholar 

  52. Jaffé, H.H.: Accounts chem. Res. 2, 136 (1969).

    Google Scholar 

  53. Klopman, G., O'Leary, B.: Fort. chem. Forsch. 15, 445 (1970).

    Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Institute of Physical Chemistry, Czechoslovak Academy of Sciences, Prague

    R. Zahradník & P. Čársky

Authors
  1. R. Zahradník
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. P. Čársky
    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

Zahradník, R., Čársky, P. Open shell cndo treatments on small and aliphatic radicals. Electronic spectra and some ground state properties. Theoret. Chim. Acta 27, 121–134 (1972). https://doi.org/10.1007/BF00528155

Download citation

  • Received:

  • Issue Date:

  • DOI: https://doi.org/10.1007/BF00528155

Keywords

Search

Navigation