The short- and long-time equilibrium transport properties of a hydrodynamically interacting suspension confined by a spherical cavity are studied via Stokesian dynamics simulations for a wide range of particle-to-cavity size ratios and particle concentrations. Many-body hydrodynamic and lubrication interactions between particles and with the cavity are accounted for utilizing recently developed mobility and resistance tensors for spherically confined suspensions (Aponte-Rivera & Zia, Phys. Rev. Fluids, vol. 1(2), 2016, 023301). Study of particle volume fractions in the range $0.05\leqslant \unicode[STIX]{x1D719}\leqslant 0.40$ reveals that confinement exerts a qualitative influence on particle diffusion. First, the mean-square displacement over all time scales depends on the position in the cavity. Additionally, at short times, the diffusivity is anisotropic, with diffusion along the cavity radius slower than diffusion tangential to the cavity wall, due to the anisotropy of hydrodynamic coupling and to confinement-induced spatial heterogeneity in particle concentration. The mean-square displacement is anisotropic at intermediate times as well and, surprisingly, exhibits superdiffusive and subdiffusive behaviours for motion along and perpendicular to the cavity radius respectively, depending on the suspension volume fraction and the particle-to-cavity size ratio. No long-time self-diffusive regime exists; instead, the mean-square displacement reaches a long-time plateau, a result of entropic restriction to a finite volume. In this long-time limit, the higher the volume fraction is, the longer the particles take to reach the long-time plateau, as cooperative rearrangements are required as the cavity becomes crowded. The ordered dynamical heterogeneity seen here promotes self-organization of particles based on their size and self-mobility, which may be of particular relevance in biophysical systems.
Changes of Conformation in Albumin with Temperature by Molecular Dynamics Simulations
