Experimental air-broadened line parameters in the\bm{ u}\textsubscript band of CH\textsubscriptD

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

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.


2004 ◽  
Vol 82 (6) ◽  
pp. 1013-1027 ◽  
Author(s):  
Robert R Gamache ◽  
Jean-Michel Hartmann

The present work is an intercomparison of experimental results on the pressure broadening and pressure shifting of water vapor absorption lines. The work focuses on application to the Earth's atmosphere; hence measurements of nitrogen, oxygen, air, and H2O as the buffer, or perturbing gas, were considered. The literature was searched and over 100 papers found. The data, measured half-widths, their temperature dependence, and the line shifts, were taken and databases created for each perturbing gas. The databases were reordered, grouping data for rovibrational transitions, and intercomparisons of the measurements made. Trends in the data, relationships between the data sets, and dependences on temperature and quantum numbers were investigated. The data were averaged and an estimated uncertainty determined. The averaged data sets are evaluated with respect to the need of the spectroscopic and remote sensing communities. Based on these studies, recommendations for new measurements are made.Key words: water vapor, half-widths, line shifts, temperature dependence of half-width.


2019 ◽  
Vol 12 (11) ◽  
pp. 6079-6089 ◽  
Author(s):  
Joshua D. Shutter ◽  
Norton T. Allen ◽  
Thomas F. Hanisco ◽  
Glenn M. Wolfe ◽  
Jason M. St. Clair ◽  
...  

Abstract. In this work, a new commercially available, laser-based, and ultra-portable formaldehyde (HCHO) gas sensor is characterized, and its usefulness for monitoring HCHO mixing ratios in both indoor and outdoor environments is assessed. Stepped calibrations and intercomparison with well-established laser-induced fluorescence (LIF) instrumentation allow a performance evaluation of the absorption-based, mid-infrared HCHO sensor from Aeris Technologies, Inc. The Aeris sensor displays linear behavior (R2 > 0.940) when compared with LIF instruments from Harvard and NASA Goddard. A nonlinear least-squares fitting algorithm developed independently of the sensor's manufacturer to fit the sensor's raw absorption data during post-processing further improves instrument performance. The 3σ limit of detection (LOD) for 2, 15, and 60 min integration times are 2190, 690, and 420 pptv HCHO, respectively, for mixing ratios reported in real time, though the LOD improves to 1800, 570, and 300 pptv HCHO, respectively, during post-processing. Moreover, the accuracy of the sensor was found to be ± (10 % + 0.3) ppbv when compared against LIF instrumentation sampling ambient air. The aforementioned precision and level of accuracy are sufficient for most HCHO levels measured in indoor and outdoor environments. While the compact Aeris sensor is currently not a replacement for the most sensitive research-grade instrumentation available, its usefulness for monitoring HCHO is clearly demonstrated.


2003 ◽  
Vol 76 (3-4) ◽  
pp. 411-434 ◽  
Author(s):  
V. Malathy Devi ◽  
D. Chris Benner ◽  
Mary Ann H. Smith ◽  
Linda R. Brown ◽  
Michael Dulick

2011 ◽  
Vol 112 (18) ◽  
pp. 2750-2761 ◽  
Author(s):  
S. Galalou ◽  
K. Ben Mabrouk ◽  
H. Aroui ◽  
F. Kwabia Tchana ◽  
F. Willaert ◽  
...  

The effect on the spectrum of a molecule of the environment in which it is located depends upon the changes which the surroundings produce in the electronic, vibrational, rotational and nuclear energies of the upper and lower states of the molecule. Studies of the influence of environment in the gaseous, liquid or solid states can thus be made by any of the appropriate techniques listed in table 1, and it is clearly desirable in studying any one system to use as many different techniques as possible. A basic difference between the effect of environment on electronic and vibra­tional energy levels arises from the very much greater overlap of electron density with the environment that results from electronic excitation. Hence while for the consideration of changes which arise in the vibrational spectrum it is adequate to consider only the distortion of the curve relating the interaction energy to the intermolecular distance in the electronic ground state, for electronic spectra, how­ever, the changes in the potential curves in both upper and lower states must clearly be taken into account. Collisions between molecules in gases lead to the broadening of rotational energy levels, and much useful information on inter­molecular force fields has resulted from observations on pressure broadening of pure rotational lines in the microwave region. Both self-broadening and broadening by different foreign gases have been studied as well as the dependence of line half­width Δ v 1/2 on the rotational quantum numbers J and K (Townes & Schawlow 1955).


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