Solvent Effects

  • Tadashi Okada
  • Hiroshi Miyasaka


Peaks in absorption and fluorescence spectra of molecules in solution are generally broader than those in the gas phase because the energy of solute molecules in a solvent is fluctuating due to the orientational fluctuations of the surrounding solvent molecules. The fluctuating motion of the solvent molecules plays an important role in chemical reactions in the solution phase. For example, in an electron transfer reaction the energy fluctuation of the reactants caused by the fluctuating solute-solvent interaction is believed to be essential to reach the transition state of that reaction. One of the most fundamental and challenging problems regarding chemical reactivity in solution is to explain how the microscopic structure and dynamics of the solute-solvent interaction can assist or impede a chemical reaction. The dynamic aspects of solvation, however, are very complex, since the orientational and translational motions of the surrounding solvent molecules occur on the same time-scale as the reactant dynamics. The most important and characteristic features of the solution phase are the types of motional degrees of freedom which are possible for both solute and solvent molecules, and which include intra- and intermolecular rotational, vibrational, or librational motion, as well as translational diffusive motion under multidimensional interaction potentials.


Solute Molecule Solvent Viscosity Generalize Langevin Equation Torsional Potential Electronic State Energy 
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.


Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.


  1. 1.
    McRae EG (1957) Theory of solvent effects on molecular electronic spectra. Frequency shifts. J Chem Phys 61:562–572CrossRefGoogle Scholar
  2. 2.
    Mataga N, Kubota T (1970) Molecular interactions and electronic specrtra. Marcel Dekker, New YorkGoogle Scholar
  3. 3.
    Cho M, Rosenthal SJ, Scherer NF, Ziegler LD, Fleming GR (1992) Ultrafast solvent dynamics: connection between time-resolved fluorescence and optical Kerr measurements. J Chem Phys 96:5033–5038CrossRefGoogle Scholar
  4. 4.
    Kahlow MA, Jarzeba W, Kang TJ, Barbara PF (1989) Femtosecond resolved solvation dynamics in polar solvents. J Chem Phys 90:151–158CrossRefGoogle Scholar
  5. 5.
    Maroncelli M, Kumar PV, Papazyan A, Horng ML, Rosenthal SJ, Fleming GR (1994) Studies of the inertial component of polar solvation dynamics. In: Gauduel Y, Rossky PJ (eds) Ultrafast reaction dynamics and solvent effects. AIP, New York, pp 310–333Google Scholar
  6. 6.
    Hirata F, Munakata T, Raineri F, Friedman HL (1995) An interaction-site representation of the dynamic structure factor of liquid and the solvation dynamics. J Mol Liq 65/66:15–22CrossRefGoogle Scholar
  7. 7.
    Hong KM, Noolandi J (1978) Solution of the Smoluchowski equation with a Coulomb potential. 1. General results. J Chem Phys 68:5163–5171CrossRefGoogle Scholar
  8. 8.
    Berne BJ, Pecora R (1976) Dynamic light scattering. Wiley, New YorkGoogle Scholar
  9. 9.
    Fleming GR (1986) Chemical applications of ultrafast spectroscopy. Oxford University Press, New YorkGoogle Scholar
  10. 10.
    Waldeck DH (1991) Photoisomerization dynamics of stilbenes. Chem Rev 91:415–436CrossRefGoogle Scholar
  11. 11.
    Kramers HA (1940) Brownian motion in a field of force and the diffusion model of chemical reactions. Physica 7:284–304CrossRefGoogle Scholar
  12. 12.
    Wortmann R, Elich K, Lebus S, Liptay W (1991) Experimental determination of the S 1 torsional potential of 9,9′-bianthryl in 2-methyl-butane by simultaneous Franck-Condon and band shape analysis of temperature-dependent optical fluorescence spectra. J Chem Phys 95:6371–6381CrossRefGoogle Scholar
  13. 13.
    Elich K, Kitazawa M, Okada T (in press) The effect of S1 torsional dynamics on the time-resolved fluorescence spectra of 9,9′-bianthryl in solution. J Phys ChemGoogle Scholar

Copyright information

© Springer-Verlag Tokyo 1998

Authors and Affiliations

  • Tadashi Okada
  • Hiroshi Miyasaka

There are no affiliations available

Personalised recommendations