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The Water Vapour Continuum: Brief History and Recent Developments

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Abstract

The water vapour continuum is characterised by absorption that varies smoothly with wavelength, from the visible to the microwave. It is present within the rotational and vibrational–rotational bands of water vapour, which consist of large numbers of narrow spectral lines, and in the many ‘windows’ between these bands. The continuum absorption in the window regions is of particular importance for the Earth’s radiation budget and for remote-sensing techniques that exploit these windows. Historically, most attention has focused on the 8–12 μm (mid-infrared) atmospheric window, where the continuum is relatively well-characterised, but there have been many fewer measurements within bands and in other window regions. In addition, the causes of the continuum remain a subject of controversy. This paper provides a brief historical overview of the development of understanding of the continuum and then reviews recent developments, with a focus on the near-infrared spectral region. Recent laboratory measurements in near-infrared windows, which reveal absorption typically an order of magnitude stronger than in widely used continuum models, are shown to have important consequences for remote-sensing techniques that use these windows for retrieving cloud properties.

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Notes

  1. The water dimer, i.e. two water molecules bound by relatively weak hydrogen bond, results in a spectrum which differs from the water monomer. In the mid and far-infrared, this absorption is predominantly due to intermolecular oscillations between the two water molecules while, in the microwave, it is due to rotation of the entire dimer (or of the monomers within the dimer). In the near-infrared, the distortion of the O–H bond (relative to its monomer state) that links the two water monomers contributes to the changes in the intramolecular vibrational spectrum. Due to the high spectral density of the dimer ro-vibrational lines, they are expected to be so strongly overlapping in atmospheric conditions that they appear as a continuum. Thus, the dimer spectrum consists of sub-bands in which heavily overlapped lines of individual stretching and bending modes have the form of a continuum.

  2. In the literature, the continuum is frequently referred to as ‘self-broadened’ and ‘foreign-broadened’, but this is presumptuous as to the cause of the continuum (as was pointed out by Cormier et al. 2005)—‘self continuum’ and ‘foreign continuum’ are more neutral and are becoming more widely adopted now.

  3. The CKD and MT-CKD models include the continua of several gases, in addition to water vapour, but the focus here will be on water vapour.

  4. This approximately corresponds to the applicability limit of the impact approximation, assuming an average duration of collision ~10−12 s.

  5. Under atmospheric conditions, the partial pressure of water dimers is typically 3 orders of magnitude lower than the vapour pressure of the monomer. The abundance of the dimer decreases with increasing temperature but the exact value of the equilibrium constant that links the abundance of dimer to the monomer, and its temperature dependence, particularly in atmospheric conditions, has significant uncertainties (see e.g., Ptashnik 2008). Note that, while higher-order clusters of water vapour likely exist, their abundance is probably too low (for example the trimer is believed to be approximately three orders of magnitude less abundant than the dimer) to have a significant radiative impact.

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Acknowledgments

This work was supported by the EPSRC/NERC CAVIAR consortium; IVP also acknowledges support from Russian National contract 02.740.11.5198. We thank the referees for their comments.

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Shine, K.P., Ptashnik, I.V. & Rädel, G. The Water Vapour Continuum: Brief History and Recent Developments. Surv Geophys 33, 535–555 (2012). https://doi.org/10.1007/s10712-011-9170-y

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