Solvent Polarity Effects on Thermodynamics and Kinetics of Intramolecular Electron Transfer Reactions

  • H. Heitele
  • S. Weeren
  • F. Pöllinger
  • M. E. Michel-Beyerle
Conference paper
Part of the The Jerusalem Symposia on Quantum Chemistry and Biochemistry book series (JSQC, volume 22)

Abstract

We present time-resolved fluorescence measurements on an intramolecular electron transfer compound in solvents of different polarity as a function of temperature. In a few solvents the free energy change of the electron transfer and its dependence on temperature and the dielectric constant of the solvent can be determined experimentally. Electron transfer rates are analyzed in terms of activation energies and preexponential factors. Both are found to depend on the polarity of the solvent. The latter is interpreted as evidence for significant entropies of activation.

Keywords

Preexponential Factor Free Energy Change Fluorescence Decay Electron Transfer Rate Butyl Acetate 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.

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References

  1. [1a]
    R. A. Marcus, J. Chem. Phys. 24, 988 (1956)Google Scholar
  2. [1b]
    R. A. Marcus, J. Chem. Phys. 43, 679 (1965).CrossRefGoogle Scholar
  3. [2a]
    N. S. Hush, Elektrochem. 61, 734 (1957)Google Scholar
  4. [2b]
    N. S. Hush, J. Chem. Phys. 28, 962 (1958)CrossRefGoogle Scholar
  5. [2c]
    N. S. Hush, Trans. Faraday Soc. 57, 557 (1961).CrossRefGoogle Scholar
  6. [3]
    A. Weller, Z. Phys. Chem. Neue Folge 133, 93 (1982).CrossRefGoogle Scholar
  7. [4]
    M. D. Newton and N. Sutin, Annu. Rev. Phys. Chem. 35, 437 (1984); and references therein.CrossRefGoogle Scholar
  8. [5]
    R. A. Marcus and N. Sutin, Biochim. Biophys. Acta 811, 265 (1985); and references therein.Google Scholar
  9. [6]
    H. Oevering, M. N. Paddon-Row, M. Heppener, A. M. Oliver, E. Cotsaris, J. W. Verhoeven, and N. S. Hush, J. Am. Chem. Soc. 109, 3258 (1987).CrossRefGoogle Scholar
  10. [7]
    J. A. Schmidt, A. Siemiarczuk, A. C. Weedon, and J. R. Bolton, J. Am. Chem. Soc. 107, 6112 (1985).CrossRefGoogle Scholar
  11. [8]
    M. D. Archer, V. P. Y. Gadzekpo, J. R. Bolton, J. A. Schmidt, and A. C. Weedon, J. Chem. Soc., Faraday Trans. 2 82, 2305 (1986).CrossRefGoogle Scholar
  12. [9a]
    L. D. Zusman, Chem. Phys. 49, 295 (1980).CrossRefGoogle Scholar
  13. [9b]
    A. B. Helman, Chem. Phys. 65, 271 (1982).CrossRefGoogle Scholar
  14. [9c]
    I. Rips and J. Jortner, J. Chem. Phys. 87, 2090 (1987).CrossRefGoogle Scholar
  15. [9d]
    H. Sumi and R. A. Marcus, J. Chem. Phys. 84, 4272 (1986)CrossRefGoogle Scholar
  16. [9e]
    H. Sumi and R. A. Marcus, J. Chem. Phys. 84, 4894 (1986).CrossRefGoogle Scholar
  17. [9f]
    A. Garg, J. N. Onuchic, and V. Ambegaokar, J. Chem. Phys. 83, 4491 (1985).CrossRefGoogle Scholar
  18. [9g]
    D. F. Calef and P. G. Wolynes, J. Phys. Chem. 87, 3387 (1983).CrossRefGoogle Scholar
  19. [9h]
    D. Huppert, V. Ittah, and E. M. Kosower, Chem. Phys. Lett. 144, 15 (1988).CrossRefGoogle Scholar
  20. [10]
    J. R. Miller and J. V. Beitz, J. Chem. Phys. 74, 6746 (1981). V. Krongauz, R. K. Huddleston and J. R. Miller, to be published.CrossRefGoogle Scholar
  21. [11]
    A. M. Oliver, D. C. Craig, M. N. Paddon-Row, J. Kroon, and J. W. Verhoeven, Chem. Phys. Lett. 150, 366 (1988).CrossRefGoogle Scholar
  22. [12]
    H. Heitele and M. E. Michel-Beyerle, J. Am. Chem. Soc. 107, 8068 (1985).CrossRefGoogle Scholar
  23. [13]
    H. Heitele, M. E. Michel-Beyerle, and P. Finckh, Chem. Phys. Lett. 134, 273 (1987).CrossRefGoogle Scholar
  24. [14]
    P. Finckh, H. Heitele, M. Volk, M. E. Michel-Beyerle, J. Phys. Chem. 92, 6584 (1988).CrossRefGoogle Scholar
  25. [15]
    H. Heitele, S. Weeren, F. Pöllinger, and M. E. Michel-Beyerle, J. Phys. Chem., in press.Google Scholar
  26. [16]
    H. Heitele, P. Finckh, and M. E. Michel-Beyerle, Angew. Chem. 101, in press.Google Scholar
  27. [17a]
    R. C. Weast, Handbook of Chemistry and Physics, CRC Press, Cleveland, 1971.Google Scholar
  28. [17b]
    J. A. Riddick and W. B. Bunger, Organic Solvents, Wiley-Interscience, New York, 1970.Google Scholar
  29. [18a]
    V. O. Levich, Adv. Electrochem. Electrochem. Eng. 4, 249 (1966).Google Scholar
  30. [18b]
    N. R. Kestner, J. Jortner, and J. Logan, J. Phys. Chem. 78, 2148 (1974).CrossRefGoogle Scholar
  31. [18c]
    R. P. Van Duyne and S. F. Fischer, Chem. Phys. 5, 183 (1974).CrossRefGoogle Scholar
  32. [18d]
    J. Ulstrup and J. Jortner, J. Chem. Phys. 63, 4358 (1975).CrossRefGoogle Scholar
  33. [19a]
    P. G. Wolynes, J. Chem. Phys. 86, 5133 (1987).CrossRefGoogle Scholar
  34. [19b]
    A. L. Nichols and D. F. Calef, J. Chem. Phys. 89, 3783 (1988).CrossRefGoogle Scholar
  35. [20a]
    I. Rips, J. Klafter, and J. Jortner, J. Chem. Phys. 88, 3246 (1988)CrossRefGoogle Scholar
  36. [20b]
    I. Rips, J. Klafter, and J. Jortner, J. Chem. Phys. 89, 4288 (1988).CrossRefGoogle Scholar
  37. [21]
    This estimate ignores specific solvent-solute interactions. Recently, the existence of a simple relation between ΔGCS and e has been questioned [8].Google Scholar
  38. [22]
    J. Jortner, J. Chem. Phys. 64, 4860 (1976).CrossRefGoogle Scholar
  39. [23]
    R. A. Marcus, J. Chem. Phys. 81, 4494 (1984).CrossRefGoogle Scholar
  40. [24a]
    R. A. Marcus and N. Sutin, Inorg. Chem. 14, 213 (1975).CrossRefGoogle Scholar
  41. [24b]
    N. Sutin in Supramolecular Photochemistry, ed. V. Balzani, NATO ASI Series C Vol. 214, D. Reidel, Dordrecht, 1987, p. 73.Google Scholar
  42. [25]
    J. N. Braddock and T. J. Meyer, J. Am. Chem. Soc. 95, 3158 (1973).CrossRefGoogle Scholar
  43. [26a]
    N. Kitamura, S. Tazuke, and S. Okano, Chem. Phys. Lett. 90 (1982) 13.CrossRefGoogle Scholar
  44. [26b]
    S. Tazuke, N. Kitamura, and Y. Kawanishi, J. Photochem. 29 (1985) 123.CrossRefGoogle Scholar
  45. [26c]
    S. Tazuke, N. Kitamura, and H.-B. Kim in Supramolecular Photochemistry, ed. V. Balzani, NATO ASI Series C Vol. 214, D. Reidel, Dordrecht, 1987, p. 87.Google Scholar

Copyright information

© Kluwer Academic Publishers 1990

Authors and Affiliations

  • H. Heitele
    • 1
  • S. Weeren
    • 1
  • F. Pöllinger
    • 1
  • M. E. Michel-Beyerle
    • 1
  1. 1.Institut für Physikalische und Theoretische ChemieTechnische Universität MünchenGarchingGermany

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