A DFT study on the structures and electronic states of zinc cluster Znn (n = 2–32)

Abstract

Ab-initio and density functional theory (DFT) calculations have been carried out for zinc clusters Znn (n = 2–32, n is the number of atoms to form a cluster) to elucidate the structure and electronic charge states of the clusters and the mechanism of clustering. The binding energies of Zn atoms were negligibly small at n = 2–3, whereas the energy increased significantly at n = 4 (the first transition). The second transition occurred at n = 8–16. In the larger clusters (n = 16–32), the binding energy increased slightly with increasing cluster size (n). The cluster size dependence of the binding energy and bond length between zinc atoms agreed well with that of the natural population of electrons in the 4p orbital of the zinc atom. In the larger clusters (n > 20), it was found that the zinc atoms in the surface region of the cluster have a positive charge, whereas those in the interior region have a negative charge with a large population in the 4p orbital. The formation mechanism of zinc clusters was discussed on the basis of the theoretical results.