Wall-mediated self-diffusion in slit and cylindrical pores

Abstract

Analytical and numerical simulation studies are performed on the diffusion of simple fluids in both thin slits and long cylindrical pores. In the region of large Knudsen numbers, where the wall-particle collisions outnumber the intermolecular collisions, we obtain analytical results for the self-diffusion coefficients for both slit and cylindrical pore shapes. The results show anomalous behavior of the mean square displacement and the velocity autocorrelation for the case of slits, unlike the case of cylindrical pores which shows standard Fick's law. Molecular dynamics simulations confirm the analytical results. We further study the wall-mediated diffusion behavior conducted by a Smoluchowski thermal wall and compare with our analytical results obtained from the stochastic thermal wall model proposed by Mon and Percus.