Anomalous Transformation of Vapor-Deposited Highly Stable Glasses of Toluene into Mixed Glassy States by Annealing Above <i>T</i><sub>g</sub>

Vapor-deposited glasses have recently emerged as a remarkable new class of materials that can form much denser and stable glasses than those obtained by cooling the liquid. These new amorphous materials reach lower regions of the energy landscape and may impact important technologies that use vapor-deposition. Here, we report on the formation of a glass with two distinct glassy states obtained through the partial annealing of highly stable vapor-deposited glassy films of toluene. The resulting glass exhibits two clear heat capacity overshoots with different onset and fictive temperatures. The transformation times of the ultrastable glass are around 10<sup>5</sup> times slower than the structural relaxation time (τ<sub>α</sub>) of supercooled liquid toluene. We show that the nature of the transformed glass depends on the annealing temperature above <i>T</i><sub>g</sub>. This finding suggests the formation of distinct supercooled liquids at temperatures slightly above <i>T</i><sub>g</sub> during the transformation of the highly stable glass. Our results are compatible with the existence of polyamorphism in toluene.