Journal of Physical Chemistry B, Vol.101, No.14, 2546-2551, 1997
Time-Dependent Stokes Shift and Its Calculation from Solvent Dielectric-Dispersion Data
The time-dependent solvation correlation function (the Stokes shift response function), which describes the solvent response to a sudden change in the charge distribution of a solute molecule, is calculated here directly from experimentally measured dielectric dispersion data, epsilon(omega), of the solvent. In the calculation a reaction field with the dielectric continuum assumption is used. This simple model is applied to the experimental results of Jimenez et al. for photoexcited coumarin and water as a solvent, and encouraging agreement is obtained using the experimental data on epsilon(omega).
Keywords:POLAR SOLVATION DYNAMICS;MOLECULAR THEORY;NONEQUILIBRIUM SOLVATION;RESOLVED FLUORESCENCE;OPTICAL-CONSTANTS;DIPOLAR LIQUIDS;RELAXATION;WATER;COUMARIN-153;SIMULATION