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STUDY OF CONTACT ION PAIR DYNAMICS IN VIEW OF THE MOLECULAR SHAPES

Han, Chul-Hee    (Dept. of Chemistry, Sun Moon Univ.  );
  • 초록

    Dynamics of contact ion-pair between 1, 2, 4, 5-tetracyanobenzene anion and cation of biphenyl derivatives was investigated on the picosecond time scale. Solvent effect on the electron transfer was observed and electron transfer rates were examined using Marcus equation which contains distance dependence of the electron transfer rate in the frequency factor, along with the consideration of molecular shape. From the discussion based on disk model for molecular shape, contribution of interring torsional motion of biphenyl to the inner-sphere reorganization energy is strongly suggested, which leads to the physical explanation for the observed solvent effect on the rate of electron transfer.


  • 참고문헌 (10)

    1. Effect of the molecular shapes of donor and the acceptor on electron transfer rates. , Kato, T.;M. Tachiya , Chem. Phys. Letters. / v.241,pp.463-468,
    2. Torsional low-frequency reorganization energy of biphenyl anion in electron transfer. , Miller, J. R.;B. P. Paulson;R. Bal;g. L. Closs , J. Phys. Chem. / v.99,pp.6923-6925,
    3. Ultrafast dynamics of sterically hindered tetraphenylmithylbutadiene in liquids. , Rucker, R. L.;B. J. Schwartz;M. A. El-Bayoumi;C. B. Harris , Chem. Phys. Letters. / v.235,pp.471-478,
    4. Substituent effects on torsional barriers:p-methoxy- and p-methoxy-p'-methyl-trans-stibene. , Siewert, s.;L. H. Spangler , J. Phys. Chom. / v.99,pp.9316-9324,
    5. Van der Waals volumes and radii. , Bondi, A. , J. Phys. Chem. / v.68,pp.441-451,
    6. Kavarnos,G. , Fundamentals of Photoinduced Electron Transfer / v.,pp.349-350,
    7. Electron transfers in chemistry and biology. , Marcus, R. A.;N. Sutin , Biochmica et Biophysica Acta / v.811,pp.265-322,
    8. Solvent effects on the energetics of intermolecular charge transfer reactions. , O'Driscoll, C.;J. D. Simon;K. S. Peters , J. Am. Chem. Soc. / v.112,pp.7091-7098,
    9. Picosecond ion-pair dynamics following CT exditation of EDA complexes of tetranitromethane with anthrecene. , Han, C. , Proc. 3rd Symp. on Laser Spectorscopy. / v.4,pp.202-212,
    10. The electron spin resonance spectrum of the biphenyl radical cation. , Courtneidge, J. L.;A. G. Davies, T. Clark;D. Wilhelm , J. Chem. Soc. Perkin trans. Ⅱ. / v.,pp.1197-1200,
  • 이 논문을 인용한 문헌 (1)

    1. 2001. "" Journal of photoscience : an international journal officail organ of the korean society of photoscience, 8(1): 33~37     

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