A DFT-Based Study of the Low-Energy Electronic Structures and Properties of Small Gold Clusters

Gold clusters Au_n of size n = 2–12 atoms were studied by the density-functional theory with an ab-initio pseudopotential and a generalized gradient approximation. Geometry optimizations starting from a number of initial candidate geometries were performed for each cluster size, so as to determine a number of possible low-energy isomers for each size. Along with the lowest-energy structures, metastable structures were obtained for many cluster sizes. Interestingly, a metastable planar zigzag arrangement of Au atoms was obtained for every cluster size n ≥ 5. The stable electronic structure, binding energy, relative stability and HOMO–LUMO gap for the lowest-energy isomer were calculated for each cluster size. Variation of the electronic properties with size is investigated in this paper and compared with experimental results and other calculations.