Molecular Cross-correlations Govern Structural Rearrangements in a Nonassociating Polar Glass Former.

Abstract

Self- and cross-correlation dynamics of deeply supercooled liquids were recently identified using photon correlation spectroscopy on the one hand and dielectric investigations on the other. These results fueled a controversial discussion whether the "generic" response identified by photon correlation spectroscopy, or rather the nonuniversal dielectric response, reflect the liquid's structural relaxation. The present study employs physical aging and oscillatory shear rheology to directly access the structural relaxation of a nonassociating glass-forming liquid and reveals that collective equilibrium fluctuations of simple liquids and not single-particle dynamics govern their structural relaxation. The present results thus challenge recent views that the glassy response of polar supercooled liquids can generically be decomposed into a Debye-type, supramolecular response and a single-particle dynamics with the latter reflecting the "true" structural relaxation. Furthermore, the current findings underscore the pivotal role dielectric spectroscopy plays in glass science as one of the rare molecular-level reorientation techniques that senses dynamical cooperativity directly.