Symmetry, Levitation Effect and Size Dependent Diffusivity Maximum

TL;DR

This paper investigates how the size and symmetry of diatomic molecules affect their diffusion maximum within zeolite Y, revealing the importance of force cancellation and the Levitation Effect in confined diffusion.

Contribution

It provides simulation evidence linking molecular symmetry and interaction strength to the presence of a diffusivity maximum in confined environments.

Findings

Symmetric diatomic molecules show a diffusivity maximum at certain bond lengths.

Weak asymmetry results in a weak diffusivity maximum.

Strong asymmetry eliminates the diffusivity maximum.

Abstract

Diffusion invariably involves motion within a medium. An universal behavior observed is that self diffusivity exhibits a maximum as a function of the size of the diffusant when the diffusant is confined to a medium, as a result of what is known as the Levitation Effect. Such a maximum in self diffusivity has been seen in widely differing medium : microporous solids, dense liquids and close-packed solids, ions in polar solvents, etc. The effect arises because the forces exerted on the diffusant by the medium in which it is confined is a minimum for the size of the diffusant for which self diffusivity is a maximum. We report here simulations on a diatomic species confined to the cages of zeolite Y. Several different simulations in which the two atoms of the model diatomic species interact with equal strength(example, $O_2$, the symmetric case) and with unequal interaction strengths (example, $CO$, asymmetric case) are modeled here. Further, the bond length of the diatomic species is varied. Our results for the symmetric case shows that self diffusivity is maximum for a large enough bond length which fits snugly into the 12-ring window of zeolite Y. For weakly asymmetric case, a weak maximum is seen as a function of the bond length of the diatomic species. However, for strongly asymmetric case, no maximum in self diffusivity is seen for all the bond lengths studied. This demonstrates close relation between symmetry and the diffusivity maximum and provides a direct evidence for the need of force cancellation to observe the Levitation Effect.