Predicting Nanoscale Dynamics of a Glass-Forming Liquid from Its Macroscopic Bulk Behavior and Vice Versa.

Abstract

The properties of a molecular liquid confined at the nanometer length scale can be very distinct from the bulk. For that reason, the macro- and the nanoscopic behaviors of glass-forming liquids are regarded as two nonconnected realms, governed by their own rules. Here, we show that the glassy dynamics in molecular liquids confined to nanometer pores might obey the density scaling relation, ργ/T, just like in bulk fluids. Even more surprisingly, the same value of the scaling exponent γ superposes the α-relaxation time measured at different state points in nanoscale confinement and upon increased pressure. We report this remarkable finding for van der Waals liquids tetramethyl-tetraphenyl-trisiloxane (DC704) and polyphenyl ether (5PPE), considered as simple, single-parameter liquids. Demonstrating that the density scaling idea can be fulfilled in both environments opens an exciting possibility to predict the dynamic features of the nanoconfined system close to its glass-transition temperature from the high-pressure studies of the bulk liquid. Likewise, we can describe the viscous liquid dynamics at any given combination of temperature and pressure based on analysis of its behavior in nanopores.