The absorption spectrum of water near 750 nm by CW-CRDS: contribution to the search of water dimer absorption

Abstract

The absorption spectrum of natural water vapour around 750 nm has been recorded with a typical sensitivity of 3 × 10⁻¹⁰ cm⁻¹ using a cw cavity ring down spectroscopy set up based on a Ti:sapphire laser. The 13 312.4–13 377.7 cm⁻¹ spectral interval was chosen as it corresponds to the region where water dimer absorption was recently measured (K. Pfeisticker et al., Science, 2003, 300, 2078–2080). The line parameters (wavenumber and intensity) of a total of 286 lines of water vapor were measured by a one by one fit of the lines to a Voigt profile. For the main water isotopologue, 276 lines were measured with line intensities as weak as 5 × 10⁻²⁹ cm molecule⁻¹i.e. about 50 times smaller than the weakest H₂¹⁶O line intensities included in the 2004 edition of the HITRAN database. On the basis of the predictions of Schwenke and Partridge, all but 16 lines could be assigned to different isotopologues of water (H₂¹⁶O, H₂¹⁸O, and HD¹⁶O) present in natural abundance in the sample. A total of 272 energy levels of H₂¹⁶O were determined and rovibrationally assigned to 18 upper vibrational states. Half of them had not been reported previously. The importance of the additional absorbance resulting from the observation of many new weak lines is discussed in relation to the detection of water dimer absorption and compared to the absorbance predicted by Schwenke and Partridge. The quality of the line parameters of water monomer is shown to be of crucial importance to identify the absorbance of the water dimer in the considered region.