Matrix reactions of alkali metal atoms with ozone: Infrared spectra of the alkali metal ozonide molecules

Abstract

The 15°K deposition of alkali metal atoms and ozone molecules at high dilution in argon produced very intense bands near 800 cm−1 and weak bands near 600 cm−1 which showed appropriate oxygen isotopic shifts for assignment to v3 and v2 of the ozonide ion. Energetic considerations and alkali metal effects clearly indicated bonding of the metal cation to the ozonide anion. The use of scrambled isotopic ozones showed that the metal cation was symmetrically bound to the ozonide anion in a C2v structure; the symmetric interionic stretching mode was observed at 281 cm−1 for Cs+O3−. The cesium-ozone reaction produced argon matrix fundamentals for CsO at 322 cm−1 and Cs2O at 457 cm−1; simultaneous mercury arc photolysis was required to yield the LiO absorption at 752 cm−1 from the lithium-ozone argon matrix reaction.