Bonding in doped gallium nanoclusters: Insights from regional DFT

Abstract

Abstract:The molecular nature (Ga 2 ) n of gallium makes this an interesting metal to investigate for the development of novel nano-materials. However, establishment of a targeted approach to manipulating the properties of gallium clusters requires a detailed understanding of how doping affects the bonding in these species. In this study, the bonding of gallium nanoclusters has been investigated using electron deformation densities and Regional Density Functional Theory (RDFT). Bonding throughout Ga 12 X clusters is generally intermediate between covalent and metallic. However, the presence of Ga 2 subunits is clearly identified in clusters with endohedral dopants (Ga 12 X, X = Al, Si, P, Ga, Ge, As).Although there is evidence of Ga 2 subunits in exohedral doped clusters, localized bonding to the dopant generally leads to significant disruption to the cluster framework. Maps of electronic chemical potential provide understanding for the observed differences in regioselectivity for hydrogen adsorption.