Water Spectra in the Region 4200–6250 cm−1, Extended Analysis of ν1+ν2, ν2+ν3, and 3ν2 Bands and Confirmation of Highly Excited States from Flame Spectra and from Atmospheric Long-Path Observations

Fourier transform measurements of water vapor line parameters in the 4200–6600cm−1 region

“…A value R ¼ 1 would mean that there is no systematic shift among two sets of data. In this sense, our intensities agree on average with those of Toth [22] within 2-3% and with those of Mikhailenko et al [19,60] within 3-4%. However, the intensities of Toth are systematically lower than ours, whereas those of Mikhailenko et al [19,60], obtained from Giessen spectra are systematically higher.…”

“…Among them, 9494 observed lines could be assigned (10,161 assigned transitions, taking into account an overlapping of some of the resulting lines) to the 4 major isotopic water species. A statistic of the lines is given in Table 2 where the number of assignments is compared to the most complete observations in this region [19,21,22] and to the HITRAN database [35]. It is seen that a progress compared to HITRAN has been mainly achieved for H 2 16 O and HDO.…”

“…These 10161 water transitions are shown band by band in Table 3 Rovibrational assignment of water lines is based on experimental energy levels known from previous studies and on global variational predictions of line positions and intensities [45,46]. The validation of the assignments and the determination of the experimental energy levels and their uncertainties for all four species were performed by using the RITZ program [47], which was successfully applied in previous studies of water spectra [19,21,48]. The observed ground state energy levels from [45] used to calculate the new upper state levels are given in Appendix A.…”

“…[18,19,21,49,50] were used to assign lines to the H 2 16 O species. Practically, for all the levels obtained from assigned transitions, the energy levels are in very 2 18 O lines, the energy levels from several experimental studies were used, namely [26] (for the (0 0 0) and (0 1 0) states), [15,28] (for the first triad of vibrational interacting states (0 2 0), (1 0 0), and (0 0 1)), [25,51] (for the second triad of vibrational interacting states (0 3 0), (1 1 0), and (0 1 1)), and [17,21,27] (for the (0 4 0), (1 2 0), and (0 2 1) states).…”

“…For the set of levels of the (1 1 0) and (0 1 1) states common to previous determinations, our values are generally very close to those reported by Toth [22], except for 4 levels of the (0 1 1) 3 8 , and 14 1 14 ) and two levels of the (1 1 0) state (6 6 1 and 6 6 0 ) where a difference amounting up to 1.27 cm À1 was observed for 8 8 The new set of experimental energies of the (0 3 0), (1 1 0), and (0 1 1) states was fitted using a rovibrational Hamiltonian for a triad of interacting states [54]. Similarly to recent works on the second triads of others water isotopic species [19,51] we used the generating function model (G-function) [55,56] for an effective Hamiltonian that takes into account resonance interactions of both anharmonic and Coriolis type. The results of the fit of the energy levels for all three states are shown in Table 6.…”