Matrix isolation infrared spectroscopic and theoretical study of group IV metal oxide clusters: M2O2 and M2O4.

Dinuclear titanium, zirconium, and hafnium oxide clusters, M2O2 and M2O4 (M = Ti, Zr, Hf) have been prepared and characterized by matrix isolation infrared spectroscopy and quantum chemical calculations. The M2O2 clusters were formed through the reactions of metal dimers and O2 in solid argon upon sample annealing. Theoretical calculations indicate that the Ti2O2 cluster has a singlet ground state with a nonplanar cyclic C(2v) structure with a strong Ti-Ti bond, while the Zr2O2 and Hf2O2 clusters have planar cyclic structures. The M2O4 clusters were characterized to have a closed-shell singlet ground state with a nonplanar C2h symmetry, which were formed from the dimerization of the metal dioxide molecules.