From Stable ZnO and GaN Clusters to Novel Double Bubbles and Frameworks

A bottom up approach is employed in the design of novel materials: first, gas-phase “double bubble” clusters are constructed from high symmetry, Th, 24 and 96 atom, single bubbles of ZnO and GaN. These are used to construct bulk frameworks. Upon geometry optimization—minimisation of energies and forces computed using density functional theory—the symmetry of the double bubble clusters is reduced to either C1 or C2, and the average bond lengths for the outer bubbles are 1.9 Å, whereas the average bonds for the inner bubble are larger for ZnO than for GaN; 2.0 Å and 1.9 Å, respectively. A careful analysis of the bond distributions reveals that the inter-bubble bonds are bi-modal, and that there is a greater distortion for ZnO. Similar bond distributions are found for the corresponding frameworks. The distortion of the ZnO double bubble is found to be related to the increased flexibility of the outer bubble when composed of ZnO rather than GaN, which is reflected in their bulk moduli. The energetics suggest that (ZnO)12@(GaN)48 is more stable both in gas phase and bulk frameworks than (ZnO)12@(ZnO)48 and (GaN)12@(GaN)48. Formation enthalpies are similar to those found for carbon fullerenes.