Clustering effects on the diffusion of patchy colloids in disordered porous media

Enskog theory is extended for the description of the self-diffusion coefficient of patchy colloidal fluid in disordered porous media. The theory includes the contact values of fluid-fluid and fluid-matrix pair distribution functions that are modified to include the dependence from the so-called probe particle porosity, φ, in order to correctly describe the effects of trapping the fluid particles by a matrix. The proposed expressions for the modified contact values of fluid-fluid and fluid-matrix pair distribution functions include three terms. Namely, a hard sphere contribution obtained by us in the previous work [Holovko M. F., Korvatska M. Ya., Condens. Matter Phys., 2020, 23, 23605], the depletion contribution connected with the cluster-cluster and cluster-matrix repulsion and the intramolecular correlation inside the cluster. It is shown that the last term leads to a remarkable decrease of the self-diffusion coefficient at a low fluid density. With a decreasing matrix porosity, this effect becomes weaker. For intermediate fluid densities, the depletion contribution leads to an increase of the self-diffusion coefficient in comparison with the hard sphere fluid. For a sufficiently dense fluid, the self-diffusion coefficient strongly decreases due to a hard sphere effect. The influence of the cluster size and the type of clusters as well as of the parameters of porous media is investigated and discussed in detail.