Thermal rotations and relaxation of vibrational energy of excited dye molecules in solution

Measurements of polarization and decay time of fluorescence of dyes in solution as a function of excitation wavelength were performed. The rate of thermal rotational depolarization was found to be independent of vibrational energy excess. To explain the observed influence of excitation wavelength on the emission anisotropy, a change in the magnitude of torsional vibrations, in addition to possible mixing of states, is proposed.