Surface diffusion in glasses of rod-like molecules posaconazole and itraconazole: effect of interfacial molecular alignment and bulk penetration

The method of surface grating decay has been used to measure surface diffusion in the glasses of two rod-like molecules posaconazole (POS) and itraconazole (ITZ). Although structurally similar antifungal medicines, ITZ forms liquid-crystalline phases while POS does not. Surface diffusion in these systems is significantly slower than in the glasses of quasi-spherical molecules of similar volume when compared at the glass transition temperature T-g. Between the two systems, ITZ has slower surface diffusion. These results are explained on the basis of the near-vertical orientation of the rod-like molecules at the surface and their deep penetration into the bulk where mobility is low. For molecular glasses without extensive hydrogen bonds, we find that the surface diffusion coefficient at T-g decreases smoothly with the penetration depth of surface molecules and the trend has the double-exponential form for the surface mobility gradient observed in simulations. This supports the view that these molecular glasses have a similar mobility vs. depth profile and their different surface diffusion rates arise simply from the different depths at which molecules are anchored. Our results also provide support for a previously observed correlation between the rate of surface diffusion and the fragility of the bulk liquid.