No abstract

Depletion interaction plays an important role in determining the structural and dynamical properties of binary colloidal mixtures. We have investigated the effect of the attractive depletion interaction between an external potential barrier and larger species in the binary mixture on the phase behavior of a binary colloidal mixture using canonical–isokinetic ensemble molecular dynamics simulations. The demixing of the binary mixture due to this depletion interaction increases as the volume fraction increases, and a pure phase of larger particles forms in the region of the potential barrier. The local density of this pure phase is high enough that a face centered cubic crystalline domain is formed at this region. This crystalline phase diffuses perpendicular to the external potential barrier, indicating that moving crystals can be obtained in an equilibrium system. The temperature dependence of diffusivity of larger particles is non-Arrhenius and changes from sub-Arrhenius to super-Arrhenius as the volume fraction increases. This crossover from sub-Arrhenius to super-Arrhenius diffusion coincides with the crystalline formation near the potential barrier.

We report results from the molecular dynamics simulations of a binary colloidal mixture subjected to an external potential barrier along one of the spatial directions at low volume fraction, ϕ = 0.2. The variations in the asymmetry of the external potential barrier do not change the dynamics of the smaller particles, showing Arrhenius diffusion. However, the dynamics of the larger particles shows a crossover from sub-Arrhenius to super-Arrhenius diffusion with the asymmetry in the external potential at the low temperatures and low volume fraction. Super-Arrhenius diffusion is generally observed in the high density systems where the transient cages are present due to dense packing, e.g., supercooled liquids, jammed systems, diffusion through porous membranes, dynamics within the cellular environment, etc. This model can be applied to study the molecular transport across cell membranes, nano-, and micro-channels which are characterized by spatially asymmetric potentials.