Wavelength-dependent rotation of dye molecules in a polar solution

Investigation of rotation movement of 3-amino-N-methylphthalimide in glycerol was carried out, taking into consideration the fluctuation of solvate structure. It was shown theoretically and experimentally that structural relaxation of the solvate shell, which follows excitation of the dye molecule, causes not only shift of the fluorescence spectrum in time but also additional rotation of the dye molecule. This effect, which may be called "wavelength-dependent rotation", depends on the light frequency of both excitation and fluorescence. In particular, at excitation near the maximum of the absorption band, when the relaxation process is followed with the red shift of the fluorescence maximum, the anisotropy of fluorescence decreases faster in the red part of the fluorescence band than in the blue part. On the contrary, in the case of far anti-Stokes excitation, when the temporal shift of fluorescence is going to the blue, the anisotropy in the red part of the spectrum drops more slowly than in the blue part. Finally, there is a special excitation frequency which causes neither change of the fluorescence maximum nor acceleration of the rotational movement of the dye molecule. It is also shown that the temporal evolution of the spectrum and anisotropy of fluorescence in a polar dye solution may be quantitatively described using the socalled inhomogeneous broadening function (IBF). This function gives the distribution of dye molecules in a solution over frequencies of pure electronic transition due to fluctuations of the surrounding shell structure. Measurements of IBF changes in time carried out for 3-amino-N-methylphthalimide showed that during first 3 ns after excitation, the half-width of the IBF grows, and at the same time its maximum quickly shifts to the red. At the later time period there are only small changes of IBF position but considerable exponential decrease in its half-width. The IBF during this period preserves the Gaussian shape.