Thermodiffusion of interacting colloids. II. A microscopic approach.

A microscopic approach is presented to describe the contribution to the thermal diffusion coefficient of colloids due to intercolloidal particle interactions. An exact expression for the leading-order virial coefficient of the thermal diffusion coefficient of interacting colloidal spheres is derived in terms of the intercolloidal pair-interaction potential and hydrodynamic interaction functions. This general expression is explicitly evaluated for hard-core interactions and for spheres with a short-ranged attractive potential. The derivation is based on a Smoluchowski equation that is generalized to include temperature gradients. For short-ranged attractive potentials, a negative Soret coefficient is predicted under certain conditions, when the depth of the attraction increases with increasing temperature.