Structure, stability, and electronic property of carbon-doped gold clusters AunC- (n=1-10): A density functional theory study

The equilibrium geometric structures, relative stabilities, and electronic properties of AunC- and Au(n+)1(-) (n = 1-10) clusters are systematically investigated using density functional theory with hyper-generalized gradient approximation. The optimized geometries show that one Au atom capped on Aun-1C- clusters is a dominant growth pattern for AunC- clusters. In contrast to Au-n+1(-) clusters, AunC- clusters are most stable in a quasi-planar or three-dimensional structure because C doping induces the local non-planarity while the rest of the structure continues to grow in a planar mode, resulting in an overall non-2D configuration. The relative stability calculations show that the impurity C atom can significantly enhance the thermodynamic stability of pure gold clusters. Moreover, the effect of C atom on the Au-n(-) host decreases with the increase of cluster size. The HOMO-LUMO gap curves show that the interaction of the C atom with Au-n(-) clusters improves the chemical stability of pure gold clusters, except for Au-3(-) and Au-4(-) clusters. In addition, a natural population analysis shows that the charges in corresponding AunC- clusters transfer from the Au-n(-) host to the C atom. Meanwhile, a natural electronic configuration analysis also shows that the charges mainly transfer between the 2s and 2p orbitals within the C atom. (C) 2013 AIP Publishing LLC.