The Continuum of Water Vapor Mixed with Methane: Absolute Absorption at 239 GHz and Linewidth Calculations.

In the aim of achieving a better understanding of the molecular mechanisms involved in the absorption continuum of the water-vapor rotational spectrum, various H(2)O-X mixtures are investigated in an atmospheric window in the mmw range. In the present study, the X mixing gas is methane. Absolute absorption rates have been measured at 239 GHz. The dependence on pressure as well as temperature has been obtained. The experimental data are compared with models using conventional line profiles. As these models require the knowledge of the collisional half-widths of H(2)O broadened by CH(4), theoretical calculations using the complex Robert-Bonamy formalism have been carried out. A "continuum effect" is observed when comparing the experimental absorption with the models, as well as for the magnitude of the absorption discrepancy and for the strong temperature dependence of this absorption. The effect is compared for various X mixing gases to the collisional broadening efficiency in the impact approximation. Copyright 2000 Academic Press.

Measurements and Calculations of the Halfwidth of Two Rotational Transitions of Water Vapor Perturbed by N2, O2, and Air.

In this paper we report the results of both an experimental and theoretical study of the halfwidths of two transitions of water vapor. Measurements on the lines of the H216O and H218O isotopomers located at 325.1 and 203.4 GHz, respectively, were carried out in the temperature range 300-393 K, with N2 and O2 as perturbing gases. The foreign-broadening coefficients and their temperature-dependence parameters were determined assuming a Voigt profile and the usual temperature dependence for the halfwidth. The retrieved values are compared to values calculated using the complex semiclassical formalism of Robert and Bonamy. The assumed intermolecular potential is a combination of electrostatic and atom-atom components. This last contribution is defined as the sum of pairwise Lennard-Jones 6-12 interactions between the atoms of H2O and the atoms of the perturbing molecules expanded to eighth order. Also calculated are the pressure-induced shifts of the spectral lines for temperatures from 200 to 400 K. Calculated and experimental results are in good agreement, within +/-3.2%, except for the N2-broadening temperature coefficients, for which there are discrepancies as high as 23%. Air-broadening parameters are determined following the classical relation: gamma (air) = 0.79gamma (N2) + 0.21gamma (O2). Copyright 1999 Academic Press.

Relaxation and Lineshape of the 500.4-GHz Line of Ozone Perturbed by N(2) and O(2).

N(2)- and O(2)-broadened linewidths of the J = 34(2,32) <-- 34(1,33) transition of ozone located at 500.4 GHz have been measured at three temperatures in the 247-295 K range by using a video-type spectrometer. Besides the Voigt profile commonly used as theoretical model for millimeter-wave investigations, different other theoretical lineshapes, the speed-dependent Voigt profile, the Galatry profile, and the speed-dependent Galatry profile, have been considered to analyze the experimental spectra, to retrieve the pressure-broadening parameters, and to give an account of the pointed out line-narrowing effect. The results for O(3) perturbed by N(2) and O(2) are finally compared to calculations based on the complex semiclassical theory of Robert and Bonamy, and with previous reported values involving the same kind of transitions. Finally, it is shown that observed line narrowings result nearly exclusively from the dependence of relaxation on molecular speeds. Copyright 2000 Academic Press.

Line Positions and Absolute Intensities in the Laser Bands of Carbon-12 Oxygen-17 Isotopic Species of Carbon Dioxide.

Infrared spectra of a carbon dioxide sample enriched with oxygen-17 have been recorded with a resolution of about 0.0025 cm-1 in the region of the laser bands near 10 and 9 µm, using the long path difference Fourier Transform Spectrometer of the LPMA in Paris. The two laser bands of the 16O12C17O and 17O12C18O species have been analyzed for the first time. Line intensities for several isotopic species have been measured in this region and the rotationless transition dipole moments and Herman-Wallis coefficients of the corresponding bands have been reported. In particular intensities, alternation in the spectra of 17O12C17O has been analyzed. Copyright 1999 Academic Press.