Matrix reactions of alkaline earth metal atoms with ozone : Infrared spectra of the metal ozonide and metal oxide molecules

The 15°K deposition of alkaline earth metal atoms and ozone molecules at high dilution in argon yielded intense bands near 800 cm⁻¹ and in the region, 450–650 cm⁻¹. The bands near 800 cm⁻¹ showed the appropriate oxygen isotopic shifts for assignment to ν₃ of the ozonide ion; the use of scrambled isotopic ozones indicated that the metal cation is symmetrically bound to the ozonide anion which contains three oxygen atoms with two equivalent oxygens. For the case of Ca and Ba atoms and ozone, infrared absorptions appeared between 450–650 cm⁻¹ which showed appropriate oxygen isotopic shifts for vibrational assignment to several metal oxide species. In the calcium experiments, bands at 635.7 and 575.5 cm⁻¹ which showed diatomic oxygen-18 isotopic shifts were tentatively identified as (CaO)₂ species; a pair of bands at 593.0 and 592.2 cm⁻¹ were tentatively assigned to CaO₂. For the barium reactions, bands at 634.7, 571.3, and 460.0 showed appropriate oxygen-18 frequency shifts for assignment to BaO, BaO₂, and (BaO)₂, respectively. The BaO assignment was confirmed by the N₂O-nitrogen matrix reaction which yielded a nitrogen matrix counterpart for BaO at 612.4 cm⁻¹.