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Characterization of Rotational Isomerization Processes in Monorotor Molecules

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Book cover Structure and Dynamics of Non-Rigid Molecular Systems

Part of the book series: Topics in Molecular Organization and Engineering ((MOOE,volume 12))

Abstract

A theoretical approach, in which the potential functions representing rotational isomerization processes are expressed in terms of linear combinations of local potentials, is presented. Partitioning the torsional potential function allows the identification of specific contributions that are at the origin of the shape of the potential curves at different regions along the torsional variable. Key properties, such as barrier heights, are then expressed parametrically in terms of properties associated to the stable conformations. Simple analytic expressions are formulated in order to explore, quantitatively and qualitatively, the main characteristics of intermediate conformers connecting the reference isomers. This procedure is used to analyse ab initio results concerning the cis-trans isomerization reaction of three series of molecules: XY-NY, OXC-CXO, and XS-SX (X =H, F, or Cl; Y = O or S). We determine the relative stabilities of the different isomers and evaluate the associated potential barriers. It is shown that the mathematical procedure used to obtain potential functions is convenient enough to be applied to more complex isomerization reactions.

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References

  1. J. Maruani, A. Hernández-Laguna and Y.G. Smeyers: J. Chem. Phys. 63 (1975) 4515; ibid. 76 (1982) 3123 [Erratum 81 (1984) 1519].

    Article  ADS  Google Scholar 

  2. J. Maruani and A. Toro-Labbé: Can. J. Chem. 66 (1988) 1948.

    Article  Google Scholar 

  3. Y.G. Smeyers: Introduction to Non-Rigid Molecule Theory, Adv. Quantum Chem., Vol. 23, Academic Press, New York (1992), pp. 1–77.

    Google Scholar 

  4. B. Pullman (ed.): Quantum Mechanics of Molecular Conformations, John Wiley & Sons, New York (1976).

    Google Scholar 

  5. A. Toro-Labbé and C. Cárdenas-Lailhacar: Int. J. Quantum Chem. 32 (1987) 685.

    Article  Google Scholar 

  6. A. Toro-Labbé: J. Mol. Struct. (Theochem) 180 (1988) 209.

    Article  Google Scholar 

  7. A. Toro-Labbé: J. Mol. Struct. (Theochem) 207 (1990) 247.

    Article  Google Scholar 

  8. C. Cárdenas-Lailhacar and A. Toro-Labbé: Theor. Chim. Acta 76 (1990) 411.

    Article  Google Scholar 

  9. (a) M. Nonella, J.R. Huber and T.K. Ha: J. Phys. Chem. 91 (1987) 5203; (b) R.P. Müller, M. Nonella, P. Russegger and J.R. Huber: Chem. Phys. 87 (1984) 351.

    Article  Google Scholar 

  10. S. Nakamura, M. Takahashi, R. Okazaki and K. Morokuma, J. Am. Chem. Soc. 109 (1987) 4142.

    Article  Google Scholar 

  11. G.E. McGraw, D.L. Bernitt and I.C. Hisatsune: J. Chem. Phys. 45 (1966) 1392.

    Article  ADS  Google Scholar 

  12. H. Jones, R.M. Badger and G.E. Moore: J. Chem. Phys. 19 (1951) 1599.

    Article  ADS  Google Scholar 

  13. C.M. Deeley and I.M. Mills: Mol. Phys. 54 (1985) 23.

    Article  ADS  Google Scholar 

  14. R.T. Hall and G.C. Pimentel: J. Chem. Phys. 38 (1963) 1889.

    Article  ADS  Google Scholar 

  15. A.P. Cox, A.H. Brittain and D.J. Finnigan: J. Chem. Soc. Faraday Trans. 61 (1971) 2179.

    ADS  Google Scholar 

  16. P.A. McDonald and J.S. Shirk: J. Chem. Phys. 11 (1982) 2355.

    Article  ADS  Google Scholar 

  17. L.A. Curtiss and V.A. Maroni: J. Phys. Chem. 90 (1986) 58.

    Article  Google Scholar 

  18. L.J. Lawlor, K. Vasudevan and F. Grein: J. Am. Chem. Soc. 100 (1978) 8062.

    Article  Google Scholar 

  19. R.E. Dodd, J.A. Rolfe and L.A. Woodward: Trans. Faraday Soc. 52 (1956) 145.

    Article  Google Scholar 

  20. A.C. Legon and D.J. Miller: J. Chem. Soc. A (1968) 1736.

    Google Scholar 

  21. R. Vance and A.G. Turner: Inorg. Chem. Acta 149 (1988) 95.

    Article  Google Scholar 

  22. D.A. Dixon and K.O. Christe: J. Phys. Chem. 96 (1992) 1018.

    Article  Google Scholar 

  23. P.N. Noble: J. Phys. Chem. 95 (1991) 4695.

    Article  Google Scholar 

  24. R.R. Smardzewski and W.F. Fox: J. Chem. Phys. 60 (1974) 2980.

    Article  ADS  Google Scholar 

  25. S.A. Sorenson and P.N. Noble: J. Chem. Phys. 11 (1982) 2483.

    Article  ADS  Google Scholar 

  26. G.N. Currie and D.A. Ramsay: Can. J. Phys. 49 (1971) 317.

    Article  ADS  Google Scholar 

  27. J.R. Durig, C.C. Tong and Y.S. Li: J. Chem. Phys. 57 (1972) 4425.

    Article  ADS  Google Scholar 

  28. A.R.H. Cole, Y.S. Li and J.R. Durig: J. Mol. Spectrosc. 61 (1976) 346.

    Article  ADS  Google Scholar 

  29. C.E. Dykstra and H.F. Schaefer: J. Am. Chem. Soc. 97 (1975) 7210.

    Article  Google Scholar 

  30. J. Tyrrel: J. Am. Chem. Soc. 98 (1976) 5456.

    Article  Google Scholar 

  31. G.R. De Maré: J. Mol. Struct. (Theochem) 107 (1984) 127.

    Article  Google Scholar 

  32. Ch.W. Bock, Y.N. Panchenko and S.V. Krasnoshchiokov: Chem. Phys. 125 (1988) 63.

    Article  Google Scholar 

  33. Ch.W. Bock and A. Toro-Labbé: J. Mol Struct. (Theochem) 232 (1991) 239.

    Article  Google Scholar 

  34. K. Kuchitsu, T. Fukuyama and Y Morino: J. Mol. Struct. 4 (1969) 41.

    Article  ADS  Google Scholar 

  35. J.R. Durig, S.C. Brown and S.E. Hannum: J. Chem. Phys. 54 (1971) 4428.

    Article  ADS  Google Scholar 

  36. J.R. Durig and S.E. Hannum: J. Chem. Phys. 54 (1971) 4428.

    Article  ADS  Google Scholar 

  37. K. Hagen and K. Hedberg: J. Am. Chem. Soc. 95 (1973) 1003.

    Article  Google Scholar 

  38. E. Herbst and G. Winnewisser: Chem. Phys. Lett. 155 (1989) 572.

    Article  ADS  Google Scholar 

  39. E. Herbst, G. Winnewisser, K.M.T Yamada, D.J. De Frees and A.D. McLean: J. Chem. Phys. 91 (1989) 5905.

    Article  ADS  Google Scholar 

  40. R.L. Kuczkowski: J. Am. Chem. Soc. 86 (1964) 3617.

    Article  Google Scholar 

  41. R.W. Davis and S. Firth: J. Mol. Spectrosc. 145 (1991) 225.

    Article  ADS  Google Scholar 

  42. E. Hirota: Bull. Chem. Soc. Japan 31 (1958) 130.

    Article  Google Scholar 

  43. A. Hinchliffe: J. Mol. Struct. 55 (1979) 127.

    Article  ADS  Google Scholar 

  44. D. Dixon, D. Zeroka, J. Wendoloski and Z. Wasserman: J. Phys. Chem. 89 (1985) 5334. F. Grein: Chem. Phys. Lett. 116 (1985) 323. T.K. Ha: J. Mol. Struct. 122 (1985) 225. C.J. Marsden and B.J. Smith: J. Phys. Chem. 92 (1988) 347.

    Article  Google Scholar 

  45. G.I. Cárdenas-Jirón, C. Cárdenas-Lailhacar and A. Toro-Labbé: J. Mol Struct. (Theochem) 210 (1990) 279.

    Article  Google Scholar 

  46. G.I. Cárdenas-Jirón, J.R. Letelier, J. Maruani and A. Toro-Labbé: Molecular Engineering 2 (1992) 17.

    Article  Google Scholar 

  47. G.S. Hammond: J. Am. Chem. Soc. 11 (1955) 334.

    Article  Google Scholar 

  48. J.E. Leffler: Science 117 (1953) 340.

    Article  ADS  Google Scholar 

  49. G.I. Cárdenas-Jirón and A. Toro-Labbé: An. Quim. 88 (1992) 43.

    Google Scholar 

  50. G.I. Cárdenas-Jirón: M.Sc. Thesis, University of Chile, Santiago (1993).

    Google Scholar 

  51. M.R. Peterson: Program Monstergauss (1977), Department of Chemistry, University of Toronto, Toronto, Ontario, Canada.

    Google Scholar 

  52. G.I. Cárdenas-Jirón and A. Toro-Labbé: Chem. Phys. Lett. 222 (1994) 8.

    Article  ADS  Google Scholar 

  53. K.W. Butz, J.R. Johnson, D.J. Krajnovich and C.S. Parmenter: J. Chem. Phys. 86 (1987) 5923.

    Article  ADS  Google Scholar 

  54. D.M. Hassett, K. Hedberg and C. Marsden: J. Phys. Chem. 91 (1993) 4670.

    Article  Google Scholar 

  55. G. Winnewisser, M. Winnewisser and W. Gordy: J. Chem. Phys. 49 (1968) 3465.

    Article  ADS  Google Scholar 

  56. G.I. Cá-Jirón, C. Cárdenas-Lailhacar and A. Toro-Labbé: J. Mol Struct. (Theochem) 282(1993) 113.

    Article  Google Scholar 

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Author information

Authors and Affiliations

  1. Centro de Mecánica Cuántica Aplicada† Departamento de Química, Facultad de Ciencias, Universidad de Chile, Casilla 653, Santiago, Chile

    Gloria I. Cárdenas-Jirón & Alejandro Toro-Labbé

  2. Department of Physical Sciences, Philadelphia College of Textiles and Science, Philadelphia, Pennsylvania, USA

    Charles W. Bock

  3. Laboratoire de Chimie Physique-Matière et Rayonnement, CNRS and UPMC, 11, rue Pierre et Marie Curie, 75005, Paris, France

    Jean Maruani

Authors
  1. Gloria I. Cárdenas-Jirón
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  2. Alejandro Toro-Labbé
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  3. Charles W. Bock
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  4. Jean Maruani
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Editor information

Editors and Affiliations

  1. CSIC, Madrid, Spain

    Yves G. Smeyers

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© 1995 Springer Science+Business Media Dordrecht

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Cárdenas-Jirón, G.I., Toro-Labbé, A., Bock, C.W., Maruani, J. (1995). Characterization of Rotational Isomerization Processes in Monorotor Molecules. In: Smeyers, Y.G. (eds) Structure and Dynamics of Non-Rigid Molecular Systems. Topics in Molecular Organization and Engineering, vol 12. Springer, Dordrecht. https://doi.org/10.1007/978-94-011-1066-2_4

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  • DOI: https://doi.org/10.1007/978-94-011-1066-2_4

  • Publisher Name: Springer, Dordrecht

  • Print ISBN: 978-94-010-4464-6

  • Online ISBN: 978-94-011-1066-2

  • eBook Packages: Springer Book Archive

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