Correlated orientational and translational motions in supercooled liquids

Abstract

We have carried out NPT molecular dynamics simulations of isolated ellipsoids in a glass forming binary mixture to gain insight into the nature of orientational relaxation (OR) in a viscous liquid. At high pressures when the liquid is highly viscous, the (OR) is found to occur mainly via correlated hopping, sometimes involving participation of several neighboring atoms, placed in a ring like tunnel. In the glassy state, hopping is found to be accompanied by larger fluctuations in the total energy and the volume of the system. Both orientational and translational hopping are found to be gated, restricted primarily by the entropic bottlenecks, with the orientational motion becoming increasingly slower than the translation as the pressure is increased. Orientational relaxation is found to occur with a wide distribution of decay times.