Temperature dependences for air-broadened Lorentz half-width and pressure shift coefficients in the 30013←00001 and 30012←00001 bands of CO2 near 1600 nm This article is part of a Special Issue on Spectroscopy at the University of New Brunswick in honour of Colan Linton and Ron Lees.

2009 ◽  
Vol 87 (5) ◽  
pp. 517-535 ◽  
Author(s):  
A. Predoi-Cross ◽  
A. R.W. McKellar ◽  
D. Chris Benner ◽  
V. Malathy Devi ◽  
R. R. Gamache ◽  
...  

In this study, 39 high-resolution spectra of pure and air-broadened CO2 recorded at temperatures between 215 and 294 K were analyzed using a multispectrum nonlinear least-squares technique to determine temperature dependences of air-broadened Lorentz half-width and air-induced pressure shift coefficients for over 100 individual 12C16O2 transitions in the 30012←00001 (at 6348 cm–1) and 30013←00001 (at 6228 cm–1) bands. Data were recorded with two different Fourier transform spectrometers (Kitt Peak FTS at the National Solar Observatory in Arizona and the Bomem FTS at NRC, Ottawa), with absorption path lengths ranging between 25 and 121 m. The sample pressures varied between 11 torr (pure CO2) and 924 torr (CO2-air) with volume mixing ratios of CO2 in air between ∼1.5% and 11% (1 torr = 133.322 4 Pa). To minimize systematic errors and increase the accuracy of the retrieved parameters, a constrained multispectrum nonlinear least-squares fitting technique was used to include theoretical quantum mechanical expressions for the rovibrational energies and intensity parameters rather than retrieving the individual positions and intensities line by line. The results suggest no detectable vibrational dependence for the temperature dependences for the air-broadened Lorentz half-width coefficients and the air-induced pressure shift coefficients. The half-width coefficients and temperature dependence exponents were modeled using semiclassical calculations based upon the Robert–Bonamy formalism. A good agreement is seen between the measurements and theoretical calculations. Beyond |m| = 26, a simple scaling factor (0.96) has been applied to the calculated half-width coefficients to match the experimental measurements.

2009 ◽  
Vol 87 (5) ◽  
pp. 499-515 ◽  
Author(s):  
D. Chris Benner ◽  
C. E. Miller ◽  
V. Malathy Devi

We report the first extensive experimental measurements of Ar-broadened half-width and pressure-induced shift coefficients, speed dependence parameters, and line mixing coefficients for the 30013←00001 and 30012←00001 bands of 16O12C16O centered near 6227 and 6348 cm–1, respectively. These parameters were determined from 15 self-broadened and six Ar-broadened CO2 spectra recorded at room temperature with long absorption path lengths (25 to 121 m) using the McMath–Pierce Fourier transform spectrometer (FTS) at the National Solar Observatory. All 21 spectra were fit simultaneously using a multispectrum nonlinear least-squares technique. The line positions and line intensities were constrained to quantum mechanical expressions to obtain maximum accuracies in the retrieved parameters. Speed-dependent line shapes with line mixing (via the relaxation matrix formalism) were required to remove systematic errors in the fit residuals using only the Voigt profile. Remaining fit residuals were minimized by adjusting the half-width and pressure-induced shift coefficients of the overlapping 31113←01101 and 31112←01101 hot bands. We compare the Ar-broadening parameters with those recently determined for self- and air-broadening in the 30012←00001 and 30013←00001 bands and also with other Ar-broadening values from the literature, as appropriate.


2007 ◽  
Vol 85 (2) ◽  
pp. 199-218 ◽  
Author(s):  
A Predoi-Cross ◽  
S Brawley-Tremblay ◽  
C Povey ◽  
M A Smith

In this study, we report the first experimental measurements of air-broadening and air-induced pressure-shift coefficients for approximately 378 transitions in the ν2 fundamental band of CH3D. These results were obtained from analysis of 17 room-temperature laboratory absorption spectra recorded at 0.0056 cm–1 resolution using the McMath–Pierce Fourier transform spectrometer located on Kitt Peak, Ariz. Three absorption cells with path lengths of 10.2, 25, and 150 cm were used to record the spectra. The total sample pressures ranged from 0.129 × 10–2 to 52.855 × 10–2 atm with CH3D volume mixing ratios of approximately 0.0109 in air. The spectra were analyzed using a multispectrum nonlinear least-squares fitting technique. We report measurements for air pressure-broadening coefficients for transitions with quantum numbers as high as J′′ = 20 and K = 15, where K′′ = K′ ≡ K (for a parallel band). The measured air-broadening coefficients range from 0.0205 to 0.0835 cm–1atm–1 at 296 K. All the measured pressure-shift coefficients are negative and are found to vary from about –0.0005 to –0.0080 cm–1 atm–1 at the temperature of the spectra. We have examined the dependence of the measured broadening and shift parameters on the J′′, and K quantum numbers and also developed empirical expressions to describe the broadening coefficients in terms of m (m = –J′′, J′′, and J′′ + 1 in the QP-, QQ-, and QR-branch, respectively) and K. On average, the empirical expressions reproduce the measured broadening coefficients to within 4.4%.PACS Nos.: 33.20.Ea, 39.30+w


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