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A limit of stability in supercooled liquid clusters

Abstract

We examine the metastable liquid phase of a supercooled gold nanocluster by studying the free energy landscape using the largest solidlike embryo as an order parameter. Just below freezing, the free energy exhibits a local minimum at small embryo sizes and a maximum at a larger 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 that we have reached a limit of stability. In contrast to the mean-field theory predictions for a spinodal, the size of the critical embryo remains finite as the limit of stability 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 on the order of kT. We suggest that this supports the idea that freezing becomes a barrierless process at low temperatures.


Publication:
Journal of Chemical Physics
Pub Date:
October 2007
DOI:

10.1063/1.2779875

Bibcode:
2007JChPh.127o4703M
Keywords:
  • 65.20.+w;
  • 61.25.Mv;
  • 64.70.Dv;
  • Thermal properties of liquids: heat capacity thermal expansion etc.;
  • Liquid metals and alloys;
  • Solid-liquid transitions
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