Melting, freezing, and coalescence of gold nanoclusters

TL;DR

This study uses molecular dynamics to explore melting, freezing, and coalescence of gold nanoclusters, revealing surface premelting, hysteresis effects, and limitations of macroscopic theories at nanoscale.

Contribution

It provides detailed insights into nanocluster behaviors, highlighting the failure of macroscopic sintering theories for facetted nanocrystals.

Findings

Surface premelting occurs before bulk melting.

Hysteresis observed in melting and freezing transitions.

Macroscopic sintering theories do not apply to nanoclusters.

Abstract

We present a detailed molecular-dynamics study of the melting, freezing, and coalescence of gold nanoclusters within the framework of the embedded-atom method. Concerning melting, we find the process to first affect the surface (``premelting''), then to proceed inwards. The curve for the melting temperature vs cluster size is found to agree reasonably well with predictions of phenomenological models based on macroscopic concepts, in spite of the fact that the clusters exhibit polymorphism and structural transitions. Upon quenching, we observe a large hysterisis of the transition temperature, consistent with recent experiments on lead. In contrast, we find macroscopic sintering theories to be totally unable to describe the coalescing behaviour of two small clusters. We attribute this failure to the fact that the nanocrystals are facetted, while the sintering theories are formulated for macroscopically smooth crystallites. The time for coalescence from our calculations is predicted to be much longer than expected from the macroscopic theory. This has important consequences for the morphology of cluster-assembled materials.