DIFFUSION ANOMALY IN SILICALITE AND VPI-5 FROM MOLECULAR-DYNAMICS SIMULATIONS

Molecular dynamics (MD) simulations on rigid and flexible framework mo dels of silicalite and a rigid framework model of the aluminophosphate VPI-5 for different sorbate diameters are reported. The sorbate-host interactions are modeled in terms of simple atom-atom Lennard-Jones in teractions. The results suggest that the diffusion coefficient exhibit s an anomaly as gamma approaches unity. The MD results confirm the exi stence of a linear regime for sorbate diameters significantly smaller than the channel diameter and an anomalous regime observed for sorbate diameters comparable to the channel diameter. The power spectra obtai ned by Fourier transformation of the velocity autocorrelation function indicate that there is an increase in the intensity of the low-freque ncy component for the velocity component parallel to the direction of motion for the sorbate diameter in the anomalous regime. The present r esults suggest that the diffusion anomaly is observed irrespective of (1) the geometry and topology of the pore structure and (2) the nature of the host material. The results are compared with the work of Derou ane and co-workers, who have suggested the existence of ''floating mol ecules'' on the basis of earlier theoretical and computational approac hes.