Revisiting the concept of activation in supercooled liquids

Abstract

AbstractIn this work, we revisit the description of dynamics based on the concepts of metabasins and activation in mildly supercooled liquids via the analysis of the dynamics of a paradigmatic glass former between its onset temperature $$T_{\mathrm{o}}$$ T o and mode-coupling temperature $$T_{\mathrm{c}}$$ T c . First, we provide measures that demonstrate that the onset of glassiness is indeed connected to the landscape, and that metabasin waiting time distributions are so broad that the system can remain stuck in a metabasin for times that exceed $$\tau _{\alpha }$$ τ α by orders of magnitude. We then reanalyze the transitions between metabasins, providing several indications that the standard picture of activated dynamics in terms of traps does not hold in this regime. Instead, we propose that here activation is principally driven by entropic instead of energetic barriers. In particular, we illustrate that activation is not controlled by the hopping of high energetic barriers and should more properly be interpreted as the entropic selection of nearly barrierless but rare pathways connecting metabasins on the landscape.