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International audience; We report revisited experimentally retrieved and theoretically calculated He-broadened Lorentz half-width coefficients and He- pressure-shift coefficients of 45 carbon monoxide transitions in the 1

International audience; We report experimental measurements and theoretical calculations for He-broadened Lorentz half-width coefficients andHe- pressure-shift coefficients of 45 carbon monoxide transitions in the 1-0 band. The high-resolution spectra analyzed inthis study were recorded over a range of sample temperatures between 296 and 80 K. The He-broadened line parameters andtheir temperature dependences were retrieved using a multispectrum nonlinear least squares analysis program. A previousanalysis of these spectra used only the Voigt line shape. In the present study four line shape models were compared includingVoigt, speed dependent Voigt, Rautian (to take into account confinement narrowing) and Rautian with speed dependence. Theline mixing coefficients have been calculated using the Exponential Power Gap scaling law. We were unable to retrieve thetemperature dependence of the line mixing coefficients. The current measurements and theoretical results are compared withother published results, where appropriate.

This paper presents the results of a spectroscopic line shape study of self- and nitrogen-broadened 12CH3D transitions in the ν3 and ν5 bands in the Triad region. We combined five pure gas spectra with eighteen spectra of lean mixtures of 12CH3D and nitrogen, all recorded with a Bruker IFS-125 HR Fourier transform spectrometer. The spectra have been analyzed simultaneously using a multispectrum nonlinear least squares fitting technique. N2-broadened line parameters for 184 transitions in the ν3 band and 205 transitions in the ν5 band were measured. In addition, line positions and line intensities were measured for 168 transitions in the ν3 band and 214 transitions in the ν5 band. We have observed 10 instances of weak line mixing corresponding to K″=3 A1 or A2 transitions. Comparisons were made for the N2-broadening coefficients and associated temperature exponents with corresponding values calculated using a semi-classical Robert Bonamy type formalism that involved an inter-molecular potential with terms corresponding to short- and long-range interactions, and exact classical molecular trajectories. The theoretical N2-broadened coefficients are overestimated for high J values, but are in good agreement with the experimental values for small and middle range J values.

The temperature-dependences of line broadening and shift parameters for many 12CH3D transitions have been determined using six high-resolution, high signal-to-noise ratio, room-temperature CH3D (98% purity) and CH3D-N2 spectra recorded with 25 cm path length ( at 0.01 cm−1 unapodized resolution) using the McMath−Pierce FTS located on Kitt Peak, Arizona, and 17 additional high quality, pure CH3D (99% purity) and CH3D-N2 spectra recorded between 79 and 296 K with the 20.38 cm path coolable cell (at 0.0056 cm−1 unapodized resolution) with the Bruker 125HR FTS at the Jet Propulsion Laboratory (JPL), Pasadena, California. The spectra have been fitted simultaneously applying a multispectrum nonlinear least-squares technique. In the analysis, the Lorentzian N2-broadened half-width coefficients and the corresponding pressure-shift coefficients as well as their temperature dependences are extracted for about 400 transitions (0≤J″≤19, K″≤16) in the perpendicular (ΔK=±1) ν6 band. At 296 K, the measured N2-broadened half-width coefficients range from 0.0209 to 0.0782 cm−1 atm−1 whereas the majority of the associated N2-induced shift coefficients are negative, and the values are between -0.016 and 0.005 cm−1 atm−1. The temperature dependence exponents for N2-broadened half-widths range between 0.264 and 0.924, whereas the temperature dependence coefficients for N2-induced shifts are between 0 and 0.00011 cm−1 atm−1 K−1. The N2-broadened half-width coefficients have been also calculated using a semi-classical approach based on a rigorous treatment of the active molecule as a symmetric top, a model intermolecular potential comprising both short- and long-range interactions, and exact classical trajectories. The role of the various high-order multipoles in the line-broadening at low, middle and high values of the rotational quantum number J″ has been investigated and the main features of the K-dependences analyzed. The calculations performed for 296, 240 and 190 K have allowed to deduce the half-width temperature-dependence exponents, completing the general comparison of our new experimental results with those which are available in the literature.

We have analyzed the methyl fluoride R Q(J,0) Q branch lines located near 1475 cm −1 using a simultaneous multi-spectrum fitting technique. In this analysis we have used previously recorded diode-laser data in which we collected many data points covering only one or two Q branch lines in a particular run. The analysis consists of simultaneously fitting 57 spectra collected with numerous pressure and path length conditions for all absorption lines. The data are concatenated to create one continuous spectrum of the Q branch. We have determined the intensity and self-broadened widths at 296 K for 23 R Q ( J ,0) lines.

We describe atmospheric validation of View the MathML source and View the MathML source CO_2 absorption coefficient databases for use by the Orbiting Carbon Observatory (OCO-2). The OCO-2 mission will collect the measurements needed to estimate column-averaged CO_2 dry air mole fraction within 1 ppm accuracy without the region- or airmass-dependent biases that would significantly degrade efforts to understand carbon sources and sinks on a global scale. To accomplish this, the forward radiative transfer model used to generate synthetic atmospheric spectra for retrievals must achieve unprecedented spectroscopic fidelity within the short wave infrared CO_2 bands sampled by the sensors. The failure of Voigt line shapes and conventional line mixing formulations for such objectives has motivated significant revisions to line shape models used to generate the gas absorption cross sections for the OCO-2 forward model. In this paper, we test line mixing and speed dependent line shapes combined with improved experimental line parameters. We evaluate pre-computed absorption coefficients in the two spectral regions of CO_2 absorbtion using high resolution FT-IR laboratory spectra, atmospheric spectra from the Total Carbon Column Observing Network (TCCON), and medium resolution soundings from the space-based Greenhouse Gases Observing Satellite (GOSAT).