Reorientational relaxation of a linear probe molecule in a simple glassy liquid

Abstract

Within the mode-coupling theory (MCT) for the evolution of structural relaxation in glass-forming liquids, correlation functions and susceptibility spectra are calculated characterizing the rotational dynamics of a top-down symmetric dumbbell molecule, consisting of two fused hard spheres immersed in a hard-sphere system. It is found that for sufficiently large dumbbell elongations, the dynamics of the probe molecule follows the same universal glass-transition scenario as known from the MCT results of simple liquids. The $α$-relaxation process of the angular-index-j=1 response is stronger, slower and less stretched than the one for j=2, in qualitative agreement with results found by dielectric-loss and depolarized-light-scattering spectroscopy for some supercooled liquids. For sufficiently small elongations, the reorientational relaxation occurs via large-angle flips, and the standard scenario for the glass-transition dynamics is modified for odd-j responses due to precursor phenomena of a nearby type-A MCT transition. In this case, a major part of the relaxation outside the transient regime is described qualitatively by the $β$-relaxation scaling laws, while the $α$-relaxation scaling law is strongly disturbed.