Diffusion of a Rouse chain in porous media: A mode-coupling-theory study.

Abstract

We use a kinetic mode-coupling theory (MCT) combining with generalized Langevin equation (GLE) to study the diffusion and conformational dynamics of a bead-spring Rouse chain (RC) dissolved in porous media. The media contains fluid particles and immobile matrix ones wherein the latter leads to the lack of translational invariance. The friction kernel ζ(t) used in the GLE can be obtained directly by adopting a simple density-functional approach in which the density correlators calculated by MCT equations of porous media serve as inputs. Due to cage effects generated by surrounding particles, ζ(t) shows a very long tail memory in the high volume fraction of fluid and matrix. It is found that the long-time center-of-mass diffusion constant D_{CM} of the RC decreases with the increment of volume fraction, influencing more strongly by the matrix particles than by the fluid ones. The auto-correlation function (ACF) of the end-to-end distance fluctuation can also be calculated theoretically based on GLE. Of particular interest is that the power-law region of ACF has a nearly fixed length in logarithmic scale when it shifts to longer time range, with increasing the volume fraction of media particles. Moreover, the effect of lack of translational invariance has been investigated by comparing the results between fluid-matrix and pure fluid cases under identical total volume fraction.