Rotational-diffusion anomalies in dye solutions from transient-dichroism experiments

Subnanosecond transient-dichroism experiments have been performed to investigate the rotational diffusion of dyes in solution. Dyes and solvents were chosen in a way to obtain information on the influence of size, shape and hydrogen-bonding abilities either of the solute or the solvent molecules. One finds slow orientational relaxation of di-anionic xanthene dyes in alcohols, while oblate cationic dyes rotate faster in spite of their comparable size. The rotational diffusion times for alcohol solutions exceed the theoretical values predicted by the Debye-Einstein model except for prolate molecules. For a solute molecule with internal mobility the rotational diffusion exhibits a partial slip behaviour. It is shown that the deviations from the Debye-Einstein model are restricted to alcohols since for other solvents either with or without strong hydrogen-bonding abilities the experimental values agree with the hydrodynamic model including the stick-boundary condition. Experiments on erythrosine B reveal the influence of size and shape of the attached solvent molecules.