We present an experimental study of the self- and N2-broadened H2 O continuum in microwindows within the ν2 fundamental centered at ~1600 cm−1. The continuum is derived from transmission spectra recorded at room temperature with a BOMEM Fourier transform spectrometer at a resolution of ~0.040 cm−1. Although we find general agreement with previous studies, our results suggest that there is significant near-wing super-Lorentzian behavior that produces a highly wave-number-dependent structure in the continuum as it is currently defined.
The continuum absorption by H2O has several characteristics that are common throughout the windows in the infrared and millimeter-wave regions. Values of the continuum absorption coefficient calculated on the basis of simple, widely used line shapes may differ greatly from observed values in the windows between strong absorption lines. The temperature dependence of this absorption is also not predictable from present day understanding of line shapes or of dieters, which may also contribute. The shapes of self-broadened H2O lines are quite different from those of N2-broadened lines, and the difference increases with increasing distance from the centers of the lines. Data obtained from laboratory samples and from atmospheric paths are presented to compare the various windows in the infrared and millimeter regions.
A far-wing line shape theory based on the binary collision and quasistatic approximations that is applicable for both the low- and high-frequency wings of the vibration-rotational bands has been developed. This theory has been applied in order to calculate the frequency and temperature dependence of the continuous absorption coefficient for frequencies up to 10,000 cm−1 for pure H2O and for H2O-N2 mixtures. The calculations were made assuming an interaction potential consisting of an isotropic Lennard-Jones part with two parameters that are consistent with values obtained from other data, and the leading long-range anisotropic part, together with the measured line strengths and transition frequencies. The results, obtained without the introduction of adjustable parameters, compare well with the existing laboratory data, both in magnitude and in temperature dependence. This leads us to the conclusion that the water continuum can be explained in terms of far-wing absorption. Current work in progress to extend the theory and to validate the theoretically calculated continuum will be discussed briefly
