Skip to main content
SpringerLink
Log in

Quantum-Chemical Analysis of Electronic Excitation and Reactivity of Olefins and Dienes

  • Published:
Russian Journal of Applied Chemistry Aims and scope Submit manuscript

Abstract

Results obtained in studying the structure of olefin and diene molecules, and complexes of these, in the ground and lower excited states by RHF, ROHF, GVB/DN, and 6-31G* quantum-chemical methods are presented. Attention is paid to the identity of the main structural and electronic parameters of triplet T 1 and singlet S 1 states forming a reactive fourfold spin-degenerate diradical equilibrium excited state (S·T)1 having the lowest energy. A new mechanism of cyclodimerization of ethylene and tetrafluoroethylene and anionic polymerization of dienes, involving the (S·T)1 states, is suggested.

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. Pedersen, S., Herek, J.L., and Zewail, A.H., Science, 1994, vol. 266, pp. 1359-1364.

    Google Scholar 

  2. Diradicals, Borden, W.T., Ed., New York: Wiley, 1982.

    Google Scholar 

  3. Benson, S.W., Thermochemical Kinetics, New York: Wiley, 1976, 2nd ed.

    Google Scholar 

  4. Kalnin'sh, K.K., Semenov, S.G., and Panarin, E.F., Dokl. Ross. Akad. Nauk, 2003, vol. 390, no. 3, pp. 350-354.

    Google Scholar 

  5. Jug, K., J. Comp. Chem., 1984, vol. 5, no. 6, pp. 555-561.

    Google Scholar 

  6. Jug, K., Tetrahedron Lett., 1985, vol. 26, no. 11, pp. 1437-1440.

    Google Scholar 

  7. Barltrop, J.A. and Coyle, J.D., Excited States in Organic Chemistry, London: Wiley, 1975.

    Google Scholar 

  8. Salem, L. and Rowland, C., Angew. Chem., Int. Ed. Engl., 1972, vol. 11, pp. 92-100.

    Google Scholar 

  9. The Exciplex, Gordon, M. and Ware, W.R., Eds., New York: Academic, 1975.

    Google Scholar 

  10. Kalnin'sh, K.K., Phys. Chem. Chem. Phys., 2001, vol. 3, no. 2, pp. 4542-4546.

    Google Scholar 

  11. Kalninsh, K.K. and Podolsky, A.F., Int. J. Quantum Chem., 2002, vol. 88, no. 5, pp. 624-633.

    Google Scholar 

  12. Buravtsev, N.N., Grigor'ev, A.S., and Kolbanovskii, Yu.A., Kinet. Kataliz, 1985, vol. 26, no. 1, pp. 7-14.

    Google Scholar 

  13. Buravtsev, N.N., Kolbanovskii, Yu.A., and Ovsyannikov, A.A., Izv. Ross. Akad. Nauk, Ser. Khim., 1995, no. 10, pp. 2048-2050.

    Google Scholar 

  14. Buravtsev, N.N. and Kolbanovskii, Yu.A., J. Fluorine Chem., 1999, vol. 96, pp. 35-42.

    Google Scholar 

  15. Buravtsev, N.N., Kolbanovskii, Yu.A., and Ovsyannikov, A.A., Zh. Prikl. Khim., 2002, vol. 75, no. 4, pp. 612-619.

    Google Scholar 

  16. Kalnin'sh, K.K., Elektronnoe vozbuzhdenie v khimii (Electronic Excitation in Chemistry), St. Petersburg: SPb. Gos. Univ. Technol. Dizaina, 1998.

    Google Scholar 

  17. Giambiagi, M., Giambiagi, M., Grempel, D.R., and Heymann, C.D., J. Chim. Phys., 1975, vol. 72, no. 1, pp. 15-22.

    Google Scholar 

  18. Giambiagi, M.S. de, Giambiagi, M., and Jorge, F.E., Z. Naturforsch., 1984, vol. 39a, pp. 1259-1273.

    Google Scholar 

  19. McWeeny, R., Rev. mod. Phys., 1960, vol. 32, no. 2, pp. 335-369.

    Google Scholar 

  20. McWeeny, R., J. Chem. Phys., 1951, vol. 19, pp. 1614-1615.

    Google Scholar 

  21. Mulliken, R.S., J. Chem. Phys., 1955, vol. 23, pp. 1833-1840.

    Google Scholar 

  22. Dmitriev, I.S. and Semenov, S.G., Kvantovaya khimiya-ee proshloe i nastoyashchee. Razvitie elektronnykh predstavlenii o prirode khimicheskoi svyazi (Quantum Chemistry: Its Past and Future, Development of Electronic Concepts of the Nature of Chemical Bond), Moscow: Atomizdat, 1980.

    Google Scholar 

  23. Mayer, I., Int. J. Quantum Chem., 1984, vol. 26, pp. 151–154.

    Google Scholar 

  24. Tulub, A.V. and Semenov, S.G., Valentnost' (Sovremennye aspekty staroi problemy) [Valence (Modern Aspects of the Old Problem)], Leningrad: Znanie, 1989.

    Google Scholar 

  25. Weeny, R.Mc. and Sutcliffe, B.T., Methods of Molecular Quantum Mechanics, London: Academic, 1969.

    Google Scholar 

  26. Schmidt, M.W., Baldridge, K.K., and Boatz, J.A., et al., J. Comput. Chem., 1993, vol. 14, no. 11, pp. 1347-1363.

    Google Scholar 

  27. Borisova, N.P. and Semenov, S.G., Vestn. Len. Gos. Univ., 1973, no. 16, pp. 119-124.

    Google Scholar 

  28. Borisova, N.P. and Semenov, S.G., Vestn. Len. Gos. Univ., 1976, no. 16, pp. 98-103.

    Google Scholar 

  29. Semenov, S.G., Valence Theory in Progress, Moscow: Mir, 1980, pp. 150-169.

    Google Scholar 

  30. Mayer, I., Chem. Phys. Lett., 1984, vol. 117, no. 4, pp. 396–396.

    Google Scholar 

  31. Dunning, T.H. and Hay, P.J., Methods of Electronic Structure Theory, Shaefer, H.F., Ed., New York: Plenum, 1977, vol. 3, pp. 1–27.

    Google Scholar 

  32. Trinquier, G. and Barthela, J.C., J. Am. Chem, Soc., 1990, vol. 112, no. 25, pp. 9121–9130.

    Google Scholar 

  33. Kalnin'sh, K.K. and Panarin, E.F., Dokl. Ross. Akad. Nauk, 2002, vol. 384, no. 3, pp. 350–354.

    Google Scholar 

  34. Kalnin'sh, K.K., Zh. Fiz. Khim., 2000, vol. 74, no. 1, pp. 117–124.

    Google Scholar 

  35. Kalnin'sh, K.K. and Podol'skii, A.F., Zh. Strukt. Khim., 2001, vol. 42, no. 6, pp. 1071–1084.

    Google Scholar 

  36. Gorner, H. and Schulte-Frohlinde, D., J. Phys. Chem., 1978, vol. 85, no. 25, pp. 2653–2659.

    Google Scholar 

  37. Caldwell, R.A. and Schwerzel, R.E., J. Am. Chem. Soc., 1972, vol. 94, no. 3, pp. 1035–1037.

    Google Scholar 

  38. Carlos, J.L., Karl, R.R., and Bauer, S.L., J. Chem. Soc., Faraday. Trans. 2, 1974, vol. 70, pp. 177–187.

    Google Scholar 

  39. Hormony, M.D., Laurie, V.W., Kuezkowski, R.L., et al., J. Phys. Chem. Ref. Data, 1979, vol. 8, pp. 619–627.

    Google Scholar 

  40. Laurie, V.W. and Pence, D.T., J. Chem. Phys., 1963, vol. 38, pp. 2693–2697.

    Google Scholar 

  41. Borisov, Yu.A., Zh. Strukt. Khim., 2002, vol. 43, no. 5, pp. 794–802.

    Google Scholar 

  42. Kalnin'sh, K.K., Zh. Prikl. Khim., 2002, vol. 75, no. 4, pp. 603–611.

    Google Scholar 

  43. Ferguson, F., Castellan, A., Deskergue, J.-P., and Bonas-Laurent, H., Chem. Phys. Lett., 1981, vol. 78, no. 3, pp. 446–450.

    Google Scholar 

  44. Atkinson, B. and Trenwith, A.B., J. Chem. Soc., 1953, pp. 2082–2087.

  45. Kalnin'sh, K.K. and Panarin, E.F., Dokl. Ross. Akad. Nauk, 1993, vol. 333, no. 1, pp. 37–39.

    Google Scholar 

  46. Kalnin'sh, K.K., Podol'skii, A.F., Kutsenko, A.D., and Semenov, S.G., Vysokomol. Soedin., Ser. A, 1990, vol. 32, no. 2, pp. 316–321.

    Google Scholar 

  47. Kalnin'sh, K.K. and Podol'skii, A.F., Vysokomol. Soedin., Ser. A, 1991, vol. 33, no. 10, pp. 2215–2224.

    Google Scholar 

  48. Kalnin'sh, K.K. and Podol'skii, A.F., Vysokomol. Soedin., 2000, vol. 42, no. 5, pp. 751–758.

    Google Scholar 

  49. Kalnin'sh, K.K. and Podol'skii, A.F., Zh. Strukt. Khim., 2000, vol. 41, no. 4, pp. 701–708.

    Google Scholar 

  50. Kalnin'sh, K.K. and Podol'skii, A.F., Zh. Strukt. Khim., 2003, vol. 44, no. 4, pp. 602–615.

    Google Scholar 

  51. Kalnin'sh, K.K. and Panarin, E.F., Dokl. Ross. Akad. Nauk, 2001, vol. 377, no. 6, pp. 786–791.

    Google Scholar 

  52. Dolgoplosk, B.A. and Tinyakova, E.I., Metalloorganicheskii kataliz v protsessakh polimerizatsii (Organometallic Catalysis in Polymerization), Moscow: Nauka, 1985.

    Google Scholar 

  53. Erusalimskii, G.B. and Lyubetskii, S.G., Protsessy ionnoi polimerizatsii (Ionic Polymerization Processes), Leningrad: Khimiya, 1974.

    Google Scholar 

  54. Monakov, Yu.B. and Tolstikov, G.A., Kataliticheskaya polimerizatsiya 1,3-dienov (Catalytic Polymerization of 1,3-Dienes), Moscow: Nauka, 1990.

    Google Scholar 

  55. Ofstead Eilert, Int. Symp. Ionic Polymerization, Paris, 1997, pp. 164–167.

  56. Erussalimsky, G.B. and Kormer, V.A., Eur. Polym. J., 1980, vol. 16, pp. 463–467.

    Google Scholar 

  57. Erusalimskii, G.B., Dolinskaya, E.R., Rozinova, O.A., and Kormer, V.A., Zh. Vses. Khim. O-va im. D.I. Mendeleeva, 1991, vol. 36, no. 1, pp. 99–105.

    Google Scholar 

  58. Sabirov, Z.M., Monakov, Yu.B., Ponomarev, O.A., et al., Zh. Fiz. Khim., 1985, vol. 59, no. 5, pp. 1136–1142.

    Google Scholar 

  59. Bondarenko, G.N. and Dolgoplosk, B.A., Vysokomol. Soedin., Ser. A, 1996, vol. 38, no. 3, pp. 464–468.

    Google Scholar 

  60. Szwarc, M. and Van Beylen, M., Ionic Polymerization and Living Polymers, New York: Chapman and Hall, 1993.

    Google Scholar 

  61. Lubnin, A.V., Osetrova, L.V., and Podkorytov, I.S., Zh. Obshch. Khim., 1989, vol. 59, no. 5, pp. 1159–1168.

    Google Scholar 

  62. Erusalimskii, B.L., Davidyan, A.A., Nikolaev, N.I., et al., Vysokomol. Soedin., Ser. A, 1983, vol. 25, no. 10, pp. 2121–2125.

    Google Scholar 

  63. Gantmakher, A.R., Vysokomol. Soedin., Ser. A, 1971, vol. 13, no. 6, pp. 1263-1277.

    Google Scholar 

  64. Arest-Yakubovich, A.A., Kristal'nyi, E.V., and Zhuravleva, I.L., Vysokomol. Soedin., Ser. B, 1994, vol. 36, no. 9, pp. 1553-1555.

    Google Scholar 

  65. Bondarenko, G.N., Sverchinskaya, S.B., Misurkin, I.A., et al., Dokl. Akad. Nauk SSSR, 1983, vol. 272, no. 1, pp. 130-135.

    Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Institute of Macromolecular Compounds, Russian Academy of Sciences, St. Petersburg, Russia

    K. K. Kalnin'sh & S. G. Semenov

  2. St. Petersburg State University, St. Petersburg, Russia

    K. K. Kalnin'sh & S. G. Semenov

Authors
  1. K. K. Kalnin'sh
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. S. G. Semenov
    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

Kalnin'sh, K.K., Semenov, S.G. Quantum-Chemical Analysis of Electronic Excitation and Reactivity of Olefins and Dienes. Russian Journal of Applied Chemistry 76, 1543–1558 (2003). https://doi.org/10.1023/B:RJAC.0000015711.78713.b5

Download citation

  • Issue Date:

  • DOI: https://doi.org/10.1023/B:RJAC.0000015711.78713.b5

Keywords

Search

Navigation