Dynamic Monte Carlo simulation of sorbate mobility in zeolites: The effects of molecular crowding on sorbate mobility

A finite lattice of adsorption sites, as shown by Monte Carlo simulation, is used to develop a simple hopping model of small molecules within the alpha cage of zeolite NaA. A two body attractive energetic interaction is employed for occupied pairs of nearest neighbor sites. A many body repulsive interaction term accounts for the crowding associated with site saturation. This term becomes important when the site-site spacing is less than the van der Waals diameter of the adsorbate. The dynamic Monte Carlo method is used to evaluate site to site hopping frequencies as a function of loading based on this potential energy function. As the sorbate-sorbate attractive interaction is increased (or, equivalently, as the temperature is reduced), mobility minima occur at certain lattice occupancies which may be explained by the formation of energetically favorable clusters on the cubocathedral lattice. In other words, molecular crowding can cause sorbate mobility to suffer minima as loading is increased. This prediction is in agreement with recent Xe NMR measurements.