Crossover between Solid-like and Liquid-like Behavior in Supercooled Liquids

TL;DR

This paper investigates the dynamic crossover in supercooled liquids between solid-like and liquid-like behaviors, identifying a characteristic temperature and proposing new pathways that explain dynamic anomalies without a thermodynamic phase transition.

Contribution

It introduces a new ratio-based characterization of supercooled liquids' dynamics and identifies a crossover temperature, providing a microscopic explanation for macroscopic anomalies.

Findings

Identification of a crossover temperature Tx between Tm and Tg.

Supercooled liquids follow paths with distinct thermodynamic and dynamic behaviors.

Simulation results show a universal crossover between solid-like and liquid-like states.

Abstract

In supercooled liquids, at a temperature between the glass transition temperature Tg and the melting point Tm, thermodynamic properties remain continuous, while dynamic behavior exhibits anomalies. The origin of such thermodynamics-dynamic decoupling has long been a puzzle in the field of glass researches. In this study, we show that the ratio of the alpha-relaxation time associated with the relative and center-of-mass coordinate of nearest-neighbor atomic pairs can effectively characterize the dynamic features of supercooled liquids. With this approach, supercooled liquids can be categorized into two distinct 'states' based on their dynamics: solid-like and liquid-like behaviors. We further propose four possible paths from the liquid to the final glass state, each exhibiting unique thermodynamic and dynamic behaviors. Two of these paths predict a characteristic temperature Tx between Tm and Tg, where a crossover between solid-like and liquid-like behaviors occurs in supercooled liquids. The molecular dynamics simulations of several supercooled liquids reveal that the actual path followed by all these systems undergo the crossover between solid-like and liquid-like behaviors. Tx is found to reside in a similar temperature range as the critical temperature Tc in the mode-coupling theory and the breakdown temperature Tb of the Stokes-Einstein relation. This crossover provides a new microscopic perspective for explaining macroscopic dynamic anomalies, and the absence of a typical thermodynamic phase transition at Tg.