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Physical vapor deposition can prepare organic glasses with high kinetic stability. When heated, these glassy solids slowly transform into supercooled liquid in a process known as rejuvenation. In this study, we anneal vapor-deposited glasses of methyl-m-toluate for 6 h at 0.98Tg to observe rejuvenation using dielectric spectroscopy. Glasses of moderate stability exhibited partial or full rejuvenation in 6 h. For highly stable glasses, prepared at substrate temperatures of 0.85Tg and 0.80Tg, the 6 h annealing time is ∼2% of the estimated transformation time, and no change in the onset temperature for the α relaxation process was observed, as expected. Surprisingly, for these highly stable glasses, annealing resulted in significant increases in the storage component of the dielectric susceptibility, without corresponding increases in the loss component. These changes are interpreted to indicate that short-term annealing rejuvenates a high frequency relaxation (e.g., the boson peak) within the stable glass. We compare these results to computer simulations of the rejuvenation of highly stable glasses generated by using the swap Monte Carlo algorithm. The in silico glasses, in contrast to the experiment, show no evidence of rejuvenation within the stable glass at times shorter than the alpha relaxation process. 

Glassy films of methyl-m-toluate have been vapor deposited onto a substrate equipped with interdigitated electrodes, facilitating in situ dielectric relaxation measurements during and after deposition. Samples of 200 nm thickness have been deposited at rates of 0.1 nm/s at a variety of deposition temperatures between 40 K and Tg = 170 K. With increasing depth below the surface, the dielectric loss changes gradually from a value reflecting a mobile surface layer to that of the kinetically stable glass. The thickness of this more mobile layer varies from below 1 to beyond 10 nm as the deposition temperature is increased, and its average fictive temperature is near Tg for all deposition temperatures. Judged by the dielectric loss, the liquid-like portion of the surface layer exceeds a thickness of 1 nm only for deposition temperatures above 0.8Tg, where near-equilibrium glassy states are obtained. After deposition, the dielectric loss of the material positioned about 5–30 nm below the surface decreases for thousands of seconds of annealing time, whereas the bulk of the film remains unchanged.