An assignment of the structured features in the Hartley band absorption spectrum of ozone

Using recent experimental data for the Hartley band absorption spectrum obtained at low temperature, a vibrational analysis of the discrete structure in the spectrum is given. It is found that all of the peaks in the range 238–292 cm can be assigned to transitions between the (0,0,0) vibrational state in the ground electronic state and (v1′,v2′) vibrational states in the upper electronic state. The observed structure in the Hartley band is due to a long progression in the symmetric stretching mode, and a shorter progression in the bending mode. Based on the vibrational assignment, the following information is obtained on the vibrational parameters and geometry of ozone in the 1B2 electronic state (all parameters are given for C2v symmetry): ω1′ = 1108 ± 25 cm−1, ω1′x1′ = 9 ± 3 cm−1, ω2′ = 298 ± 12 cm−1, ω3′ = (1650 ± 300)i cm−1, r00=0.140±0.002 nm, φ=105±2°. The analysis that is presented demonstrates that residual vibrational structure can occur in dissociative transitions, confirming previous suggestions.