Entropic Necks, Dynamic Crossovers, and Fragility in Supercooled Liquids

Abstract

The dramatic slowdown of dynamics in supercooled liquids is accompanied by a sequence of dynamical crossovers, most notably the transition from high-temperature collision-dominated transport to low-temperature activated structural relaxation. A particularly striking manifestation of this change is the crossover from Rosenfeld excess-entropy scaling to the Adam--Gibbs relation. In this work we develop a theoretical framework based on a configuration-space extension of Zwanzig's entropic-neck picture and combine it with a Mori--Zwanzig memory-function formalism to address anomalies of supercooled liquids. The central idea is that structural relaxation is controlled by the narrowing of configurational pathways connecting metastable basins of the inherent-structure landscape. Starting from coupled slow variables describing intrabasin motion and neck fluctuations, we derive a reduced generalized Langevin description in which elimination of the neck coordinate generates a long-lived memory kernel and naturally leads to entropy-controlled activated dynamics. At high temperatures the neck is broad and readily accessible, yielding Rosenfeld-type transport governed primarily by local structural entropy. Upon cooling, progressive neck constriction produces an increasing entropy deficit, leading to Adam--Gibbs behavior and activated relaxation. Within this picture, fragility acquires a simple geometric interpretation: fragile liquids are characterized by a rapid collapse of the effective configurational neck with decreasing temperature, whereas strong liquids exhibit a much slower evolution of accessible pathways. The framework does not by itself compute the configurational entropy, mismatch penalty, or cooperative length from microscopic interactions; its aim is to provide a dynamical and geometrical interpretation.