title: Transport in nanoporous zeolites: relationships between sorbate size, entropy, and diffusivity.
abstract: Molecular dynamics simulations have been performed on monatomic sorbates confined within zeolite NaY to obtain the dependence of entropy and self-diffusivity on the sorbate diameter. Previously, molecular dynamics simulations by Santikary and Yashonath [J. Phys. Chem. 98, 6368 (1994)], theoretical analysis by Derouane et al. [J. Catal. 110, 58 (1988)] as well as experiments by Kemball [Adv. Catal. 2, 233 (1950)] found that certain sorbates in certain adsorbents exhibit unusually high self-diffusivity. Experiments showed that the loss of entropy for certain sorbates in specific adsorbents was minimum. Kemball suggested that such sorbates will have high self-diffusivity in these adsorbents. Entropy of the adsorbed phase has been evaluated from the trajectory information by two alternative methods: two-phase and multiparticle expansion. The results show that anomalous maximum in entropy is also seen as a function of the sorbate diameter. Further, the experimental observation of Kemball that minimum loss of entropy is associated with maximum in self-diffusivity is found to be true for the system studied here. A suitably scaled dimensionless self-diffusivity shows an exponential dependence on the excess entropy of the adsorbed phase, analogous to excess entropy scaling rules seen in many bulk and confined fluids. The two trajectory-based estimators for the entropy show good semiquantitative agreement and provide some interesting microscopic insights into entropy changes associated with confinement.
authors.affiliation: Solid State and Structural Chemistry Unit, Indian Institute of Science, Bangalore 560 012, India.
authors.forename: Bhaskar J
authors.initials: BJ
authors.lastname: Borah
authors.forename: Prabal K
authors.initials: PK
authors.lastname: Maiti
authors.forename: Charusita
authors.initials: C
authors.lastname: Chakravarty
authors.forename: S
authors.initials: S
authors.lastname: Yashonath