Dynamics of swelling/contracting hard spheres surmised by an irreversible Langevin equation

The diffusion of molecules through uniform homogeneous materials can readily be described by Brownian motion or generalizations thereof. The further generalization of these models to describe molecular diffusion through heterogeneous and nonstationary solvents is much less understood. Phenomenological nonstationary generalizations of the generalized Langevin equation (GLE) have earlier been developed satisfying the fluctuation-dissipation relationship in quasi-equilibrium limits while exhibiting somewhat complex behavior away from equilibrium. This reduced-dimensional representation should be capable of describing the diffusion of a particle through a colloidal suspension whose average particle size is tuned by an external driving force such as pH. A simple particle model of such a process involves the motion of a hard-sphere particle in an explicit environment of swelling hard spheres. The velocity autocorrelation functions observed in a large number of simulations of the particle model under various swelling rates agree precisely with those of a single form of the nonstationary phenomenological model. Though this procedure is not an explicit projection of the mechanical system onto the nonstationary GLE, it does show that the latter correctly describes the dynamics of the projected coordinate--namely, diffusion of the solute--under nonequilibrium conditions. Both nonequilibrium solvent models lead to behavior reminiscent of beta-relaxation processes at packing fractions substantially below that of the glass transition.