Contribution to the Analysis of the3A2←X1A1“Wulf” Transition of Ozone by High-Resolution Fourier Transform Spectrometry

Ab initio characterization of low-lying triplet state potential-energy surfaces and vibrational frequencies in the Wulf band of ozone

“…Both the electronic and vibrational assignments were later placed on firm experimental footing by high-resolution spectroscopic analysis of the rotational structure of several low-lying vibrational features. [8][9][10][11][12][13][14] It is now well established that there are three low-lying triplet ( 3 B 2 , 3 A 2 , and 3 B 1 ) states that are involved in the Wulf band absorption. [5][6][7][15][16][17] Absorption to the 3 B 2 state can be neglected because of extremely small oscillator strength.…”

“…15 Other outstanding questions include the mechanism and dynamics of the observed predissociation of nearly all the rovibrational levels. [11][12][13] Apparently, such questions cannot be answered definitively without a clear picture of the three-dimensional topology of the relevant PESs and the nonadiabatic interaction between the 3 A 2 and 3 B 1 states.…”

A new graphical version of STROTAB: The analysis and fitting of singlet–triplet spectra of asymmetric top molecules in the prolate or oblate limits

“…In some molecules with a large number of incorrectly sorted lines, the least squares procedure may fail completely. One such molecule is ozone [4], which, although considered a case (b) type molecule, is sufficiently removed from pure case (b) to cause difficulties. The least squares fitting for this molecule was hampered not only by the above mentioned K sorting problems but also by the diffuseness of a large portion of the spectrum.…”

“…Application of the progression sorting method eliminated the problem and allowed for a stable least-squares fit to any desired J value. The spectrum of ozone [4] provides an additional test. As mentioned earlier, it was clear during the course of our rotational analysis of the molecule that the program was incorrectly labeling some high J levels for a small number of branches and these lines could not be included in the fit.…”

“…If the correct pattern was not found, then the eigenvalue labels were re-evaluated using the 'least-ambiguous' method outlined by Pickett [3]. For a large number of J values and for most molecules this revised sorting will work satisfactorily but we did find considerable difficulties in using this method for the ozone molecule [4]. This was first noticed when the higher members of a hitherto regular branch progression had its quantum labels swapped with another branch member.…”