A Limit of Stability in Supercooled Liquid Clusters

TL;DR

This study investigates the stability limit of supercooled gold nanoclusters by analyzing free energy landscapes, revealing a finite critical embryo size at the spinodal and a transition to barrierless freezing.

Contribution

It provides the first detailed free energy analysis of the stability limit in supercooled nanoclusters, challenging mean-field predictions.

Findings

Identification of a finite critical embryo size at the spinodal.

Observation of a transition to barrierless freezing near the spinodal.

Demonstration of rapid nucleation rate increase as free energy barrier diminishes.

Abstract

We examine the metastable liquid phase of a supercooled gold nanocluster by studying the free energy landscape using the largest solid-like embryo as an order parameter. Just below freezing, the free energy exhibits a local minimum at small embryo sizes and a maximum at larger embryo sizes which denotes the critical embryo size. At T=660K the free energy becomes a monotonically decreasing function of the order parameter as the liquid phase becomes unstable, indicating we have reached a spinodal. In contrast to the usual mean-field theory predictions, the size of the critical embryo remains finite as the spinodal is approached. We also calculate the rate of nucleation, independently from our free energy calculations, and observe a rapid increase in its temperature dependence when the free energy barrier is in the order of $kT$. This supports the idea that freezing becomes a barrierless process around the spinodal temperature.