Bridging the Gap Between the Mode Coupling and the Random First Order Transition Theories of Structural Relaxation in Liquids

Abstract

A unified treatment of structural relaxation in a deeply supercooled glassy liquid is developed which extends the existing mode coupling theory (MCT) by incorporating the effects of activated events by using the concepts from the random first order transition (RFOT) theory. We show how the decay of the dynamic structure factor is modified by localized activated events (called instantons) which lead to the spatial reorganization of molecules in the region where the instanton pops up. The instanton vertex added to the usual MCT depicts the probability and consequences of such an event which can be derived from the random first order transition theory. The vertex is proportional to $exp(-A/s_{c})$ where $s_{c}$ is the configurational entropy. Close to the glass transition temperature, $T_{g}$, since $s_{c}$ is diminishing, the activated process slows beyond the time window and this eventually leads to an arrest of the structural relaxation as expected for glasses. The combined treatment describes the dynamic structure factor in deeply supercooled liquid fairly well, with a hopping dominated decay following the MCT plateau.