Dynamical heterogeneity and the interplay between activated and mode coupling dynamics in supercooled liquids

Abstract

We present a theoretical analysis of the dynamic structure factor (DSF) of a liquid at and below the mode coupling critical temperature T_c, by developing a self-consistent theoretical treatment which includes the contributions both from continuous diffusion, described using general two coupling parameter (F₁₂) mode coupling theory (MCT), and from the activated hopping, described using the random first order transition (RFOT) theory, incorporating the effect of dynamical heterogeneity. The theory is valid over the whole temperature plane and shows correct limiting MCT like behavior above T_c and goes over to the RFOT theory near the glass transition temperature, T_g. Between T_c and T_g, the theory predicts that neither the continuous diffusion, described by pure mode coupling theory, nor the hopping motion alone suffices but both contribute to the dynamics while interacting with each other. We show that the interplay between the two contributions conspires to modify the relaxation behavior of the DSF from what would be predicted by a theory with a complete static Gaussian barrier distribution in a manner that may be described as a facilitation effect. Close to T_c, coupling between the short time part of MCT dynamics and hopping reduces the stretching given by the F₁₂-MCT theory significantly and accelerates structural relaxation. As the temperature is progressively lowered below T_c, the equations yield a crossover from MCT dominated regime to the hopping dominated regime. In the combined theory the dynamical heterogeneity is modified because the low barrier components interact with the MCT dynamics to enhance the relaxation rate below T_c and reduces the stretching that would otherwise arise from an input static barrier height distribution. Many of these results can be explained from an analytical treatment of the combined equation of motion.