Near wall dynamics of a spherical particle in crowded suspensions of colloidal rods - dynamic information from TIRM...

We performed total internal reflection microscopy (TIRM) experiments to determine the depletion potentials between probe spheres and a flat glass wall which are induced by long and thin, rod-shaped colloids (fd-virus), and probe the spatially resolved dynamics of the probe spheres. The dynamic information from the same raw TIRM intensity time traces is extracted in three different ways: by determining the spatially averaged diffusion constant of the probe sphere normal to the wall, by measuring the position dependence of the diffusion coefficient, and by measuring the particle's local drift velocity. Up to a concentration of about 6 times the overlap concentration of the rod-like colloids, the spatially averaged diffusion coefficient and the amplitude of the depletion potential are in surprisingly good agreement with theoretical predictions in which mutual interactions between the rods are neglected, that is, where the concentration is less than the overlap concentration. On increasing the depletant content even further, however, both the static and the averaged dynamic quantities begin to deviate from such theoretical predictions. In particular we find large deviations from the prediction by Mao, Cates, and Lekkerkerker [J. Chem. Phys., 1997, 106, 3721] based on the third order virial expansion for the rod concentration. It is shown that there are significant inaccuracies in TIRM measurements of diffusion coefficients due to the limited time range in which the mean squared displacements vary linearly in time, whereas mean displacements give much more accurate information concerning the probe sphere dynamics.