Molecular dynamics simulations have been used to study diffusion of n-hexane in wholly amorphous poly(ethylene-stat-octene)s with comonomer contents ranging from 0 to 11.5 mol%. The branches in the polymer increased the specific volume by affecting the packing of the chains in the rubbery state in accordance with experimental data. The diffusion of n-hexane at penetrant concentrations between 0.5 and 9.1 wt% was simulated within time-scales between 0.1 and 0.2 mu s. The penetrant diffusivity unexpectedly decreased with increasing comonomer content. The penetrant molecule motion statistics showed that systems with high comonomer content showed a greater tendency for short distance motion (over a sampling period of 3 ps) whereas the systems with lower comonomer content showed penetrant motion over longer distances. It seems that the branches retarded local chain mobility of the polymer thereby trapping the penetrant molecules. All systems studied showed a minimum in penetrant diffusivity at ca. 1 wt% n-hexane and a marked increase in diffusivity at higher penetrant concentrations. The volumetric data for the different polymer-penetrant systems were consonant with additional volumes of the different components. Comparison between simulated diffusivities (for a wholly amorphous polymer) and experimentally obtained diffusivity data for semicrystalline polymers showed that constraining effect of the crystals were substantial for the highly crystalline systems and that it gradually decreased with decreasing crystallinity. (c) 2007 Elsevier Ltd. All rights reserved.