Matrix infrared spectra and density functional calculations of TiO3 and TiO5 in solid argon

The reaction of titanium monoxide molecules and 02 was studied by using matrix isolation infrared spectroscopy as well as theoretical calculations. The titanium monoxide molecule reacts with O-2 to form TiO3 spontaneously on annealing. The TiO3 molecule is characterized to be a side-on bonded peroxo titanium monoxide complex, (eta(2)-O-2)TiO, which has a nonplanar C-s symmetry with a (1)A' ground state. The (eta(2)-O-2)TiO complex can further coordinate another dioxygen to give TiO5, a disuperoxo titanium monoxide complex, (eta(2)-O-2)(2)TiO, which possesses a (3)A '' ground state and a nonplanar C-s geometry.