Effect of encaged aromatic guests on the shape and connectivity of molecular cavity in crystalline polystyrene evaluated by molecular simulations.

The delta form of crystalline syndiotactic polystyrene is a clathrate molecular compound in which various aromatic molecules are encaged. We have investigated the size, shape, and connectivity of the molecular cavity in the crystal using a molecular dynamics simulation. The effects of the guest species on the cavity structure were investigated in detail. In order to systematically vary the guest structure, various aromatic guests, e.g., benzene, toluene, p-xylene, m-xylene, o and mesitylene were examined. The interstitial spaces between the guests and the polymer chains were analyzed by cluster analysis of the free volumes. The individual cavity volumes into which the guests are clathrated were also evaluated. It was found that the guest molecules can greatly affect not only the cavity size and shape but also the connectivity of the cavities. The transport of small molecules in the crystal is discussed in connection with the cavity structure.