On the validity of Stokes–Einstein–Debye relations for rotational diffusion in colloidal suspensions

Abstract

According to the Stokes–Einstein–Debye (SED) relation, the rotational diffusion coefficient of a colloidal tracer sphere scales with the inverse of the solvent viscosity. Here we investigate the generalization of the SED relation to tracer diffusion in suspensions of neutral and charged colloidal host spheres. Rotational diffusion coefficients are measured with dynamic light scattering and phosphorescence spectroscopy, and calculated including two- and three-particle hydrodynamic interactions. We find that rotational tracer diffusion is always faster than predicted by the SED relation, except for large tracer/host size ratios λ. In the case of neutral particles this observation is rationalized by introducing an apparent λ-dependent slip boundary coefficient. For charged spheres at low ionic strength, large deviations from SED scaling are found due to the strongly hindered host sphere dynamics. Finally, we present some first experiments on tracer sphere diffusion in suspensions of host rods, showing that hydrodynamic hindrance by rods is much stronger than by spheres. We conclude by pointing to some interesting unresolved issues for future research.