Finite Temperature Behavior of Small Silicon and Tin Clusters: An Ab Initio Molecular Dynamics Study

Abstract

The finite temperature behavior of small Silicon (Si$_{10}$, Si$_{15}$, and Si$_{20}$) and Tin (Sn$_{10}$ and Sn$_{20}$) clusters is studied using isokinetic Born-Oppenheimer molecular dynamics. The lowest equilibrium structures of all the clusters are built upon a highly stable tricapped trigonal prism unit which is seen to play a crucial role in the finite temperature behavior of these clusters. Thermodynamics of small tin clusters (Sn$_{10}$ and Sn$_{20}$) is revisited in light of the recent experiments on tin clusters of sizes 18-21 [G. A. Breaux et. al. Phys. Rev. B {\bf 71} 073410 (2005)]. We have calculated heat capacities using multiple histogram technique for Si$_{10}$, Sn$_{10}$ and Si$_{15}$ clusters. Our calculated specific heat curves have a main peak around 2300 K and 2200 K for Si$_{10}$ and Sn$_{10}$ clusters respectively. However, various other melting indicators such as root mean square bond length fluctuations, mean square displacements show that diffusive motion of atoms within the cluster begins around 650 K. The finite temperature behavior of Si$_{10}$ and Sn$_{10}$ is dominated by isomerization and it is rather difficult to discern the temperature range for transition region. On the other hand, Si$_{15}$ does show a liquid like behavior over a short temperature range followed by the fragmentation observed around 1800 K. Finite temperature behavior of Si$_{20}$ and Sn$_{20}$ show that these clusters do not melt but fragment around 1200 K and 650 K respectively.