Complex dynamics in nanoscale phase separated supercooled liquids

Abstract

The relaxation properties of supercooled As_{x}S_{100−x} liquids are investigated using a combination of infrared photon correlation spectroscopy and topological constraint theory. Results reveal two channels of relaxation for sulfur-rich compositions that manifest by an unusual profile in the density-density autocorrelation function involving two typical timescales. This indicates a reduced temperature-dependent dynamics for one of the channels associated with a sulfur-rich segregated nanoscale phase that furthermore displays a low liquid fragility. Conversely, the dynamics of the emerging cross-linked As-S network is associated with a growth of the glass transition temperature with As content. These results can be quantitatively understood from topological constraint theory applied to a phase separated network for which a dedicated constraint enumeration must be achieved. The vanishing of this peculiar behavior occurs close to the reported isostatic reversibility window observed at the glass transition.