Resonance Raman spectrum and vibrational analysis of the ozonide ion in the argon matrix-isolated M+O3− species

Abstract

Beams of alkali metal atoms and ozone molecules at high dilution in argon were condensed on a tilted copper wedge at 16°K and were examined by argon and krypton plasma laser excitation. Very intense bands shifted 1010 cm−1 below the exciting lines showed small alkali metal effects and appropriate oxygen-18 shifts for assignment to the v1 symmetric oxygen-oxygen mode of the ozonide ion in the M+O3− species. The intense fundamental and a regular progression of overtones out to 4v1 suggest that these spectra are probably due to the resonance Raman effect. Vibrational analysis for six isotopic ozonide species produced the oxygen-oxygen force constant 4.18 ± 0.11 mdyn/Å. The spectroscopic value for the heat of atomization of the ozonide ion calculated from the vibrational constants ω1 = 1028.2 cm−1 and X11 = 4.95 cm−1 for Cs+O3− is 153 kcal/mole, which agrees well with the thermodynamic value.