A line-by-line calculation of the continuum absorption coefficient with the wing line contour describing the absorption in different windows outside of the water vapor bands in the 4000–8000 cm-1 spectral region is presented. The continuum absorption calculated with the line wing contour characterizing the absorption in the 5800–6400 cm-1 window is shown to be close to the total absorption. Hence it follows that the absorption in the 5000–5500 cm-1 and 6900–7700 cm-1 bands is almost entirely due to metastable dimers and free complexes.
Experimental Н2О self-continuum (T =296 K) versus predicted absorption spectra of bound and metastable dimers1 and present calculations for the 5200–5500 cm-1 band. The black dots are the experimental data, the triangles are the stable dimer absorption coefficients, and the gray curves represent the calculated results using the κLorχ line shape.
Recent laboratory observations and advances in theoretical quantum chemistry allow a reappraisal of the fundamental mechanisms that determine the water vapour self-continuum absorption throughout the infrared and millimetre wave spectral regions. By starting from a framework that partitions bimolecular interactions between water molecules into free-pair states, true bound and quasi-bound dimers, we present a critical review of recent observations, continuum models and theoretical predictions. In the near-infrared bands of the water monomer, we propose that spectral features in recent laboratory-derived self-continuum can be well explained as being due to a combination of true bound and quasi-bound dimers, when the spectrum of quasi-bound dimers is approximated as being double the broadened spectrum of the water monomer. Such a representation can explain both the wavenumber variation and the temperature dependence. Recent observations of the self-continuum absorption in the windows between these near-infrared bands indicate that widely used continuum models can underestimate the true strength by around an order of magnitude. An existing far-wing model does not appear able to explain the discrepancy, and although a dimer explanation is possible, currently available observations do not allow a compelling case to be made. In the 8–12 μm window, recent observations indicate that the modern continuum models either do not properly represent the temperature dependence, the wavelength variation, or both. The temperature dependence is suggestive of a transition from the dominance of true bound dimers at lower temperatures to quasi-bound dimers at higher temperatures. In the mid- and far-infrared spectral region, recent theoretical calculations indicate that true bound dimers may explain at least between 20% and 40% of the observed self-continuum. The possibility that quasi-bound dimers could cause an additional contribution of the same size is discussed. Most recent theoretical considerations agree that water dimers are likely to be the dominant contributor to the self-continuum in the mm-wave spectral range.
