Density functional analysis of the structural evolution of Ga-n (n=30-55) clusters and its influence on the melting characteristics

摘要

Recent experimental results have reported surprising variations in the shapes of the heat capacity curves and melting temperatures of gallium clusters in the size range of 30-55 atoms [G. A. Breaux , J. Am. Chem. Soc. 126, 8628 (2004)]. In the present work, we have carried out an extensive density functional investigation on ten selected clusters in the above mentioned size range. In particular, we have analyzed the ground state geometry and the nature of bonding in these clusters using electron localization function. We demonstrate that the existence or otherwise of a large island of atoms bonded with similar strength (i.e., the local order) in the ground state geometry is responsible for the variation in the shape of the heat capacity curve. We attribute the observed higher melting temperatures of some of the clusters (viz., Ga-45-Ga-48) to the presence of a distinct core and strong covalent bonds between the core and surface atoms. The present work clearly demonstrates that it is possible to understand the general trends observed in the heat capacity curves across the entire series on the basis of the analysis of their ground state.