About 200 pure water-vapor spectra covering the region from 800 to 3500 cm−1 were recorded with resolution of 0.1 cm−1 at temperatures 311, 318, 325, 339, 352, and 363 K using a 2 m base White cell coupled to the BOMEM DA3.002 FTIR spectrometer. The water-vapor pressure varied from 28 to 151 mbar (21–113 Torr). Under these conditions, the continuum absorbance is quite measurable with the available path lengths up to 116 m. A program was developed for spectral processing that calculates, fits, and removes ro-vibrational structure from the spectrum. The spectra obtained were used to retrieve averaged and smoothed binary absorption coefficients over the region from 800 to 1250 cm−1. Our continuum data extrapolated to room temperature are in reasonable agreement with the MT_CKD continuum model. But at higher temperatures the MT_CKD model provides very low values, which are up to 50% less than those experimentally measured.
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Water continuum CO2 laser absorption spectra are reported for temperatures between 27 and -10°C. The continuum is found to possess a negative temperature coefficient. The results obtained suggest that the magnitude of this temperature coefficient increases with increasing water pressure and decreasing temperature. The temperature coefficients between 27 and 10°C for air mixtures containing 3.0- and 7.5-Torr water vapor are -2.0 ± 0.4 and -2.9 d 0.5%/ C, respectively. For mixtures with 3.0-Torr water the 10-O°C temperature coefficient is -7.7 ± 0.2%/°C. The temperature and water pressure dependencies observed for the continuum suggest that while both collisional broadening and water dimer mechanisms contribute to the continuum, the dimer mechanism is more important over this temperature range.
