Fourier transform and high sensitivity cw-cavity ringdown absorption spectroscopies of ozone in the 6030–6130 cm −1 region. First observation and analysis of the 3 ν1+3 ν3 and 2 ν2+5 ν3 bands

Abstract

The absorption spectrum of 16O 3 has been recorded between 6030 and 6130 cm −1 by Fourier Transform Spectroscopy (GSMA, Reims) and cw-cavity ringdown spectroscopy (LSP, Grenoble). The two new bands 3 ν 1+3 ν 3 and 2 ν 2+5 ν 3 centered at 6063.923 and 6124.304 cm −1, respectively are observed and analyzed. Rovibrational transitions with J and K a values up to 40 and 10, respectively, could be assigned. The rovibrational fitting of the observed energy levels shows that some rotational levels of the (303) and (025) bright states are perturbed by interaction with the (232), (510) and (124) dark states. The observed energy levels could be reproduced with a rms deviation of 5×10 −3 cm −1 using a global analysis based on an effective Hamiltonian including the five interacting states. The energy values of the three dark vibrational states provided by the fit are found in good agreement with theoretical predictions. The parameters of the resulting effective Hamiltonian and of the transition moment operator retrieved from the measured absolute line intensities allowed calculating a complete line list of 2035 transitions, available as Supplementary Material. The integrated band strengths are estimated to be 1.22×10 −24 and 3.15×10 −24 cm −1/(mol cm −2) at 296 K for the 3 ν 1+3 ν 3 and 2 ν 2+5 ν 3 bands, respectively. A realistic error for these band strengths is 15% (see text).