Long-Wavelength Fluctuations in Quasi-2D Supercooled Liquids.

ABSTRACT

We use molecular simulation to characterize the dynamics of supercooled liquids confined in quasi-2D slit geometries. Similar to bulk supercooled liquids, the confined systems exhibit subdiffusive dynamics on intermediate time scales arising from particle localization inside their neighbor cages, followed by an eventual crossover to diffusive behavior as cage rearrangement occurs. The quasi-2D confined liquids also exhibit signatures of long-wavelength fluctuations (LWFs) in the lateral directions parallel to the confining walls, reminiscent of the collective displacements observed in 2D but not 3D systems. The magnitude of the LWFs increases with the lateral dimensions of systems with the same particle volume fraction and confinement length scale, consistent with the logarithmic scaling predicted for 2D Mermin-Wagner fluctuations. The amplitude of the fluctuations is a nonmonotonic function of the confinement length scale because of a competition between caging and strengthening LWFs upon approaching the 2D limit. Our findings suggest that LWFs may play an important role in understanding the behavior of confined supercooled liquids due to their prevalence over a surprisingly broad range of particle densities and confinement length scales.