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.
Papers with the following subject areas are suitable for publication in the Journal of Quantitative Spectroscopy and Radiative Transfer:
As the world’s leading publisher of science and health information, Elsevier serves more than 30 million scientists, students, and health and information professionals worldwide. We are proud to play an essential role in the global science and health communities and to contribute to the advancement of these critical fields. By delivering world-class information and innovative tools to researchers, students, educators and practitioners worldwide, we help them increase their productivity and effectiveness. We continuously make substantial investments that serve the needs of the global science and health communities.
This is a comprehensive study of water-vapor line and continuum absorption in the 8–14μm atmospheric window by laser-photoacoustic spectroscopy. The characteristics of laser-photoacoustic spectroscopy and detectors are discussed with results on continuum and line absorption at selected CO2-laser wavelengths.
We have assigned four weak absorption lines which occur at the CO2-laser emissions 10P(40), 10R(20), 9P(38) and 9R(36) to pure rotational transitions of H2O, and have determined the dependence of the continuum water-vapor absorption over the temperature range +70°C and −20°C. The measured negative temperature coefficient of the continuum is consistent with both monomer and dimer models, yet not with predictions of larger water clusters.
Experiments with supersaturated water vapor indicate that for S ⩾ 1 collision broadening of distant strong lines as well as water dimer absorption contribute to the continuum. However, the dimer absorption is an order of magnitude too small to cause a significant contribution at ambient atmospheric conditions.
We have investigated the effect of UV-radiation on the 8–14μm absorption of water vapor, buffered either with N2 or synthetic air. The observed changes are explained by UV-photodissociation of H2O molecules and by ozone production. There is no evidence in favor of a cluster model.
Finally, we compared our measured spectra with LOWTRAN 6 and HITRAN models. The LOWTRAN yields a stronger negative temperature dependence than observed while the HITRAN does not predict the observed continuum absorption.
