Ab initio Molecular Dynamical Investigation of the Finite Temperature Behavior of the Tetrahedral Au$_{19}$ and Au$_{20}$ Clusters

TL;DR

This study uses ab initio molecular dynamics to compare the finite temperature behaviors of Au19 and Au20 gold clusters, revealing size and defect-dependent melting transitions and atomic rearrangements.

Contribution

It demonstrates that structural defects, like missing atoms, significantly influence melting behavior and phase transition characteristics in gold clusters.

Findings

Au20 exhibits a sharp solid-liquid transition around 770 K.

Au19 shows a broad, continuous melting transition due to atomic rearrangements.

Defects can cause broad melting transitions, not just disorder or symmetry loss.

Abstract

Density functional molecular dynamics simulations have been carried out to understand the finite temperature behavior of Au$_{19}$ and Au$_{20}$ clusters. Au$_{20}$ has been reported to be a unique molecule having tetrahedral geometry, a large HOMO-LUMO energy gap and an atomic packing similar to that of the bulk gold (J. Li et al., Science, {\bf 299} 864, 2003). Our results show that the geometry of Au$_{19}$ is exactly identical to that of Au$_{20}$ with one missing corner atom (called as vacancy). Surprisingly, our calculated heat capacities for this nearly identical pair of gold cluster exhibit dramatic differences. Au$_{20}$ undergoes a clear and distinct solid like to liquid like transition with a sharp peak in the heat capacity curve around 770 K. On the other hand, Au$_{19}$ has a broad and flat heat capacity curve with continuous melting transition. This continuous melting transition turns out to be a consequence of a process involving series of atomic rearrangements along the surface to fill in the missing corner atom. This results in a restricted diffusive motion of atoms along the surface of Au$_{19}$ between 650 K to 900 K during which the shape of the ground state geometry is retained. In contrast, the tetrahedral structure of Au$_{20}$ is destroyed around 800 K, and the cluster is clearly in a liquid like state above 1000 K. Thus, this work clearly demonstrates that (i) the gold clusters exhibit size sensitive variations in the heat capacity curves and (ii) the broad and continuous melting transition in a cluster, a feature which has so far been attributed to the disorder or absence of symmetry in the system, can also be a consequence of a defect (absence of a cap atom) in the structure.