Diffusion of Aromatics in Silicalite-1: Experimental and Theoretical Evidence of Entropic Barriers

A specific computational methodology based on transition state theory (Kolokathis, P. D. et al. Mol. Simul., 2014, 40, 80–100) is evolved and applied for calculation of the self-diffusion coefficients of p -xylene and benzene in silicalite-1 at infinite dilution. In addition, we study the orientational distributions of phenyl rings and methyl stems of p -xylene and benzene sorbed in the zeolite and check for the existence of entropic barriers to translational motion. A new reduction method for the states appearing in the free energy profiles is presented and used for calculation of transition rate constants for elementary jumps. Quasi-elastic neutron scattering measurements are also conducted and compared with the simulation results. A major conclusion from both experiments and simulations is that p -xylene diffuses roughly 100 times faster than benzene when sorbed at low occupancy in silicalite. Benzene encounters strong entropic barriers to translational motion at channel intersections, where it can adopt a variety of orientations. The corresponding barriers for p -xylene are much lower, reflecting the inability of its major axis to reorient within channel intersections.