Melting, freezing, and coalescence of gold 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 first to 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 behavior of two small clusters. We attribute this failure to the fact that the nanocrystals are faceted, 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.