The Huggins band of ozone: assignment of hot bands.

The "hot bands" of the Huggins band of ozone are assigned, in both the 218 K and the 295 K spectrum. The assignment is based on intensities calculated with three-dimensional vibrational wave functions for the electronic ground state (X) and the excited state (B). The hot-band structures in the 218 K spectrum all can be assigned to transitions starting from vibrational states with one quantum of stretching excitation in the ground electronic state. The 295 K spectrum shows new structures, which are due to transitions originating from vibrational states in the X state with two quanta of excitation of the stretching modes--despite very small Boltzmann factors. All structures in the low-energy range of the 295 K spectrum, even the very weak ones, thus can be uniquely interpreted. The significance of hot bands results from the strong increase of Franck-Condon factors with excitation of the stretching modes in both the lower and/or the upper electronic states, whose equilibrium bond lengths differ significantly.

Spectroscopy and predissociation of the 3A2 electronic state of ozone 16O3 and 18O3 by high resolution Fourier transform spectrometry.

A high resolution Fourier transform spectrometry analysis of the rotational structure of the 2(0)1 absorption bands of the 3A2<--X1A1 Wulf transition for the isotopomers 16O3 and 18O3 of the ozone molecule is presented. These bands are very intense compared to the 0(0)0 bands but the predissociation is so strong that the main sub-bands appear as continuous contours. Isolated lines and band contour methods are used together to analyse these two rovibrational bands. The lines corresponding to the F2 component are generally the most intense and isolated. Our data sets for the (0 1 0) level of the 3A2 state are limited to about 102 weakly or unperturbed rotational lines for the 2(0)1 of 16O3 in the range 9620-10,140 cm(-1) and 123 weakly or unperturbed rotational lines for the same band of 18O3. Using for each of them the well-defined ground state parameters, we obtained a standard deviation of about 0.035 cm(-1) in the fit to the lines for 16O3 and 0.027 cm(-1) in the case of 18O3. The rotational constants A, B and C, the three rotational distortion terms deltaK, deltaJK and deltaJ, the spin-rotation constants a0, a and b have been successfully calculated for 16O3 and 18O3 while the spin-spin constants were fixed to their respective values obtained for the origin bands. As is the case for the 0(0)0 band, we have a partial agreement with the isotopic laws for the rotational constants. The geometrical parameters of the (0 1 0) level of 3A2 state for the two isotopomers are close, r = 1.357 A, theta = 100.7 degrees for 18O3 and r = 1.352 A and theta = 100.0 degrees for 16O3. The origin of the 2(0)1 band of 18O3 is red shifted by 7.06(4) cm(-1) with respect to 16O3 2(0)1 band and the two bending mode quanta are, respectively, 528.99(9) and 501.34(7) cm(-1). A preliminary qualitative analysis of the predissociation is given in the particular case of the F2 spin component of 16O3 for 0(0)0 and 2(0)1 bands by the measurement of shifts of positions of some rovibrational levels and the evolution of predissociation broadenings in (Q)Q2 branches. We justify the existence of perturbations in the rovibrational levels of 3A2 state through different interaction types: with the dissociation continuum of the same electronic state or with high vibrational repulsive or weakly bound levels of the ground state.

Contribution to the Analysis of the 3A2 <-- &Xtilde;1A1 "Wulf" Transition of Ozone by High-Resolution Fourier Transform Spectrometry.

The analysis of the rotational structure of the high-resolution Fourier transform 0(0)0 absorption spectrum of the 3A2 <-- &Xtilde;1A1 band system of the "Wulf" transition of the isotopomer 16O3 of ozone is reported for the first time. With a near pure case (b) coupling model for the upper triplet state, we have assigned a significant portion of the spectrum, mainly the F1 (J = N + 1) and F2 (J = N) spin components, primarily in the lower frequency region of the band. The lines corresponding to the F3 (J = N - 1) component are weak at lower frequencies and heavily congested in the central and higher frequency regions of the spectrum. Perturbations and predissociation phenomena have reduced the effective lifetime of the metastable 3A2 state and have also limited the number of transitions included in the least-squares fit of the band. Approximately 100 lines have been assigned in the range from 9100-9550 cm-1. Three rotational, three centrifugal distortion, three spin-rotation, and one spin-spin constant were varied. The geometry of the molecule in the 3A2 state, as determined from these constants, is r = 1.345 Å and theta = 98.9 degrees, in good agreement with ab initio results. Copyright 1998 Academic Press.