Study on the Mixed ZnO Clusters and Ring-Like ZnO Ions

The pure Zn m ( m = 2–10), mixed Zn m O m ( m = 1–10), Zn m O 10− m ( m = 1–9) clusters and the univalent and divalent ring-like Zn m O m ( m = 2–10) cluster ions are systematically investigated by using Amsterdam density functional (ADF) program with Triple-zeta with two polarization functions basis set in conjunction with self-consistent field. Our calculated results show that the Zn 4 and Zn 7 clusters are the magic clusters. The structures of the Zn m O m ( m = 1–10) clusters evolve from two-dimension to three-dimension after m = 8. For the Zn m O 10− m ( m = 1–9) clusters, the Zn-rich structures evolve gradually from three-dimension to plane with an increase in the O ratios. The Zn 5 O 5 cluster with equal ratio has a two dimensional structure. In the O-rich clusters, the O dimers can be easily detached from them. The O and Zn atoms partly adopt sp 2 and sp hybridization, respectively, in the ring-like Zn m O m ( m = 2–10) clusters and their ions. Gain and loss charge would affect the degree of hybridization and change their geometries. Their structural changes can be explained by valence bond theory.