Orientational and Translational Hopping in Supercooled Liquids and Glasses : Correlated Dynamics in a Free Energy Landscape

Abstract

Orientational relaxation (OR) in a viscous, glassy liquid is investigated by carrying out extensive NPT molecular dynamics simulations of isolated ellipsoids in a glass forming binary mixture. Near the glass transition, the OR occurs mainly via hopping involving either a ring- or a tunnel like motion, with the participation of several neighboring atoms. 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 {\it gated}, restricted primarily by the entropic bottlenecks, with orientation becoming increasingly slower than translation as the pressure is increased. OR is heterogeneous, with a wide distribution of decay times.