Structures, growth modes and spectroscopic properties of small zirconia clusters

Equilibrium geometries, electronic energies and crystal growth modes of small (ZrO2)n (n⩽6,n=8) clusters have been studied systematically by density functional calculation. Using the ground state structures and electronic energies obtained from our calculations, we found four kinds of structural growth modes (cube-like, ring-like, top-angle-like and chain-like) for (ZrO2)n (n⩽6) clusters. Theoretical analyses of the HOMO-LUMO gaps and the infrared spectra show that the cube-like growth mode prevails, and the peak of about 500 cm−1 is ascribed to the characteristic vibration of cubic zirconia based on the theoretical and experimental investigation, as well as the previous experimental results.