Robert McPheat

Recommended isolated-line profile for representing high-resolution spectroscopic transitions (IUPAC Technical Report)

Abstract The report of an IUPAC Task Group, formed in 2011 on “Intensities and line shapes in high-resolution spectra of water isotopologues from experiment and theory” (Project No. 2011-022-2-100), on line profiles of isolated high-resolution rotational-vibrational transitions perturbed by neutral gas-phase molecules is presented. The well-documented inadequacies of the Voigt profile (VP), used almost universally by databases and radiative-transfer codes, to represent pressure effects and Doppler broadening in isolated vibrational-rotational and pure rotational transitions of the water molecule have resulted in the development of a variety of alternative line-profile models. These models capture more of the physics of the influence of pressure on line shapes but, in general, at the price of greater complexity. The Task Group recommends that the partially Correlated quadratic-Speed-Dependent Hard-Collision profile (pCqSD-HCP) should be adopted as the appropriate model for high-resolution spectroscopy. For simplicity this should be called the Hartmann–Tran profile (HTP). The HTP is sophisticated enough to capture the various collisional contributions to the isolated line shape, can be computed in a straightforward and rapid manner, and reduces to simpler profiles, including the Voigt profile, under certain simplifying assumptions.

Water vapor self‐continuum absorption in near‐infrared windows derived from laboratory measurements

In most near-infrared atmospheric windows, absorption of solar radiation is dominated by the water vapor self-continuum and yet there is a paucity of measurements in these windows. We report new laboratory measurements of the self-continuum absorption at temperatures between 293 and 472 K and pressures from 0.015 to 5 atm in four near-infrared windows between 1 and 4 m (10000-2500 cm-1); the measurements are made over a wider range of wavenumber, temperatures and pressures than any previous measurements. They show that the self-continuum in these windows is typically one order of magnitude stronger than given in representations of the continuum widely used in climate and weather prediction models. These results are also not consistent with current theories attributing the self continuum within windows to the far-wings of strong spectral lines in the nearby water vapor absorption bands; we suggest that they are more consistent with water dimers being the major contributor to the continuum. The calculated global-average clear-sky atmospheric absorption of solar radiation is increased by 0.75 W/m2 (which is about 1% of the total clear-sky absorption) by using these new measurements as compared to calculations with the MT_CKD-2.5 self-continuum model.

Water vapour foreign-continuum absorption in near-infrared windows from laboratory measurements

For a long time, it has been believed that atmospheric absorption of radiation within wavelength regions of relatively high infrared transmittance (so-called ‘windows’) was dominated by the water vapour self-continuum, that is, spectrally smooth absorption caused by H2O−H2O pair interaction. Absorption due to the foreign continuum (i.e. caused mostly by H2O−N2 bimolecular absorption in the Earths atmosphere) was considered to be negligible in the windows. We report new retrievals of the water vapour foreign continuum from high-resolution laboratory measurements at temperatures between 350 and 430 K in four near-infrared windows between 1.1 and 5 μm (9000–2000 cm−1). Our results indicate that the foreign continuum in these windows has a very weak temperature dependence and is typically between one and two orders of magnitude stronger than that given in representations of the continuum currently used in many climate and weather prediction models. This indicates that absorption owing to the foreign continuum may be comparable to the self-continuum under atmospheric conditions in the investigated windows. The calculated global-average clear-sky atmospheric absorption of solar radiation is increased by approximately 0.46 W m−2 (or 0.6% of the total clear-sky absorption) by using these new measurements when compared with calculations applying the widely used MTCKD (Mlawer–Tobin–Clough–Kneizys–Davies) foreign-continuum model.

Airborne and satellite remote sensing of the mid-infrared water vapour continuum.

Remote sensing of the atmosphere from space plays an increasingly important role in weather forecasting. Exploiting observations from the latest generation of weather satellites relies on an accurate knowledge of fundamental spectroscopy, including the water vapour continuum absorption. Field campaigns involving the Facility for Airborne Atmospheric Measurements research aircraft have collected a comprehensive dataset, comprising remotely sensed infrared radiance observations collocated with accurate measurements of the temperature and humidity structure of the atmosphere. These field measurements have been used to validate the strength of the infrared water vapour continuum in comparison with the latest laboratory measurements. The recent substantial changes to self-continuum coefficients in the widely used MT_CKD (Mlawer–Tobin–Clough–Kneizys–Davies) model between 2400 and 3200 cm−1 are shown to be appropriate and in agreement with field measurements. Results for the foreign continuum in the 1300–2000 cm−1 band suggest a weak temperature dependence that is not currently included in atmospheric models. A one-dimensional variational retrieval experiment is performed that shows a small positive benefit from using new laboratory-derived continuum coefficients for humidity retrievals.

Large-volume, coolable spectroscopic cell for aerosol studies

We have constructed a coolable spectroscopic cell for characterizing the physical and chemical properties of simulated atmospheric aerosol particles. The cell is designed for experiments in which the refractive indices, freezing temperatures, and the phase and chemical composition of a wide range of aerosol types are measured. The relatively large volume (0.075 m(3)) of the cell reduces wall-aerosol interactions and allows the aerosol residence time to exceed 2 h. The cell has been optically interfaced to Fourier-transform spectrometers to record broadband infrared, visible, and ultraviolet extinction spectra of aerosol particles and gas-phase components over a range of temperatures (180-300 K). The data generated with the cell have applications in remote sensing, radiative transfer models, heterogeneous atmospheric chemistry, and pollution studies.

Absolute intensities in the ν1, 2ν2, 2ν3 + ν4 band system of carbonyl fluoride

The IR spectrum of carbonyl fluoride, COF 2 , has been measured in the region 1880–1980 cm −1 using a Bomem Fourier transform spectrometer under 0.005 cm −1 resolution at a gas pressure of 3.2 Torr, 10 cm pathlength and at room- and stratospheric (ca. 200 K) temperatures. In this region the ν 1 band at 1945 cm −1 dominates the spectrum and is in Fermi resonance with the weaker 2ν 2 band at 1914 cm −1 , and in B-type Coriolis resonance with the 2ν 3 + ν 4 band at 1936 cm −1 . The absorption coefficients of this band system have been determined from the experimental spectra and the integrated intensity in this region is found to be 3.07 × 10 −17 cm molecule −1 at room temperature and 3.26 × 10 −17 cm molecule −1 at ca. 200 K. Using calculated spectra the integrated intensities were predicted to be 2.90 × 10 −17 cm molecule −1 and 3.01 × 10 −17 cm molecule −1 , respectively using transition dipole moments of 0.1592 D for ν 1 and 0.1097 D for 2ν 2 .† The small discrepancy in integrated intensity can be accounted for from thermally populated states, whose contribution was not calculated.