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Recently Fakhraai and coworkers measured surface diffusion in ultrastable glass produced by vapor deposition, ordinary glass with and without physical aging, and ultrathin films of the same molecular glass-former, N,N'-bis(3-methylphenyl)-N,N'-diphenylbenzidine (TPD). Diffusion on the surfaces of all these glasses is greatly enhanced compared with the bulk diffusion similar to that previously found by others, but remarkably the surface diffusion coefficients D S measured are practically the same. The observed independence of D S from changes of structural α-relaxation due to densification or finite-size effect has an impact on the current understanding of the physical origin of enhanced surface diffusion. We have demonstrated before and also here that the primitive relaxation time τ 0 of the coupling model, or its analogue τ β , the Johari-Goldstein β-relaxation, can explain quantitatively the enhancement found in ordinary glasses. In this paper, we assemble together considerable experimental evidence to show that the changes in τ β and τ 0 of ultrastable glasses, aged ordinary glasses, and ultrathin-films are all insignificant when compared with ordinary glasses. Thus, in the context of the explanation of the enhanced surface diffusion given by the coupling model, these collective experimental facts on τ β and τ 0 further explain approximately the same D S in the different glasses of TPD as found by Fakhraai and coworkers.

Why is surface diffusion the same in ultrastable, ordinary, aged, and ultrathin molecular glasses?