Competitive Freezing in Gold Nanoparticles

We use molecular dynamics simulations to study the freezing of gold nanoparticles in a size range of N = 309-923 gold atoms and find the clusters freeze to a variety of structures, including icosahedra, decahedra and face-centered cubic type structures. Measurements of the rate of freezing for the different structures reveal that the icosahedral clusters form an order of magnitude faster than the remaining structures over the entire range of cluster sizes studied. An analysis of the structural evolution of the icosahedral and decahedral clusters during freezing events suggests that, despite the vast difference in freezing rates, the two structures both initially form the same five-fold symmetric cap, constructed from tetrahedral sub-units of face-centered cubic packed atoms. The slow rate of decahedron freezing may be caused introduction of strain into the structure as it grows along the five-fold symmetric axis of the cluster and the need to form high energy < 100 > facets.