Physical interpretation of the partition function for colloidal clusters

Abstract

Colloidal clusters consist of small numbers of colloidal particles bound by weak, short-range attractions. The equilibrium probability of observing a cluster in a particular geometry is well-described by a statistical mechanical model originally developed for molecules. To explain why this model fits experimental data so well, we derive the partition function classically, with no quantum mechanical considerations. Then, by comparing and contrasting the derivation in particle coordinates with that in center-of-mass coordinates, we physically interpret the terms in the center-of-mass formulation, which is equivalent to the high-temperature partition function for molecules. We discuss, from a purely classical perspective, how and why cluster characteristics such as the symmetry number, moments of inertia, and vibrational frequencies affect the equilibrium probabilities.