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Positions and intensities for transitions in the 1←0 bands of the four CO isotopologues (12C16O, 13C16O, 12C18O and 13C18O) were retrieved from analyses of spectra of different low-pressure pure samples and high-pressure air-broadened mixtures (1940–2260 cm−1) in two different multispectrum fittings involving selected groups of 21 (for 13C16O) and 20 (for 12C18O) spectra. Air-broadened half-width and air-shift coefficients, their temperature dependences, line mixing via off-diagonal relaxation matrix element coefficients for CO-air collision systems, and quadratic speed dependence parameters were measured for 13C16O and 12C18O transitions. In both the fittings, two low-pressure room-temperature spectra of a high purity natural sample of CO recorded with the Kitt Peak FTS were included to retrieve the positions and intensities of 12C16O transitions. All other spectra in the fittings were obtained with either 13C-enriched or 18O-enriched samples using the JPL Bruker IFS-125HR FTS. Four absorption cells with path lengths between 0.5131(5) and 20.38(2) cm were used to record the data. The cells are temperature controlled, except for the shortest cell. Positions and intensities for the 1←0 band transitions were determined from the retrieved ro-vibrational constants (G, B, D and H), band intensity and Herman-Wallis parameters by applying the theoretical quantum mechanical expressions. The band strengths of 12C16O, 12C18O and 13C18O are very close (∼0.3%) to HITRAN2012 values but for 13C16O the band strength is ∼4.8% larger than the HITRAN2012 and 2.6% larger than the HITRAN2016 value.

A Bruker IFS-120HR Fourier transform spectrometer located at the Pacific Northwest National Laboratory (PNNL) in Richland, Washington was used to record a series of spectra of pure H2O and air-broadened H2O in the regions of the ν1 and ν3 bands (3450–4000 cm−1) at different pressures, temperatures and volume mixing ratios of H2O in air. Eighteen high-resolution, high signal-to-noise (S/N) ratio absorption spectra were recorded at T = 268, 296 and 353 K using two temperature-controlled absorption cells with path lengths of 9.906(1) and 19.95(1) cm. The resolution of the spectra recorded with the 9.906 cm and 19.95 cm absorption cells was 0.006 and 0.008 cm−1, respectively. A multispectrum nonlinear least squares fitting technique was employed to fit all the eighteen spectra simultaneously to retrieve 313 accurate line positions, 315 intensities, 229 Lorentz air-broadened half-width and 213 air-shift coefficients and their temperature dependences (136 for air-broadened width and 128 for air-shift coefficients, respectively). Room temperature self-broadened half-width coefficients for 209 transitions and self-shift coefficients for 106 transitions were also measured. Line mixing coefficients were experimentally determined for isolated sets of 10 transition pairs for H2O-air and 8 transition pairs for H2O-H2O using the off-diagonal relaxation matrix element formalism, and 85 quadratic speed dependence parameters were measured. Modified Complex Robert-Bonamy (MCRB) calculations of self-, and air-broadened (from N2- and O2-broadening) half-width and air-shift coefficients, and temperature dependence exponents of air-broadened half-width coefficients are made. The measurements and calculations are compared with each other and with similar parameters reported in the literature.

Pure CO2 spectra recorded at room temperature and different pressures (0.2–140 Torr) have been analyzed with the help of a fitting routine that takes into account asymmetries arising in the spectral lines due to pressure induced effects such as line mixing. The fitting procedure used in this study allows one to adjust the ro-vibrational constants for the band rather than fitting for individual line parameters. These constrained parameters greatly reduce the measurement uncertainties and allow us to observe the behavior of the weak lines corresponding to high J quantum numbers. We have also calculated line mixing parameters using approximations based on exponential nature of the energy difference between ground and upper vibrational states involved in the ro-vibrational band transitions. The calculated results show good agreement when compared with the experimentally determined parameters.

We report experimental measurements of spectral line shape parameters (air-broadened width, shift, and line mixing coefficients) for several transitions in the ν3 Q branch of methane in the 3000–3023 cm−1 region. 13 high-resolution, room temperature laboratory spectra of pure methane and air-broadened methane recorded with two different Fourier transform spectrometers are fitted. 12 of these spectra were acquired at 0.01 cm−1 resolution with the McMath-Pierce FTS at the National Solar Observatory on Kitt Peak, and one higher-resolution (∼0.0011 cm−1) low pressure methane spectrum was obtained with the Bruker IFS-120HR FTS at the Pacific Northwest National Laboratory, in Richland, Washington. All the spectra were obtained using high purity natural samples of CH4 and lean mixtures of the same natural CH4 in dry air. For the 12 spectra recorded at Kitt Peak, three different absorption cells (L = 5, 25 and 150 cm) were used while the methane spectrum at PNNL was obtained using a 19.95 cm long absorption cell. For the analysis, an interactive multispectrum nonlinear least squares fitting software was employed where all the 13 spectra were fitted simultaneously. An accurate and self-consistent set of line parameters were determined by constraining a few of those for severely blended transitions. Line mixing was measured for 14 transition pairs for the CH4-air collision system. A constant speed dependence parameter, consistent with measured speed dependence values obtained in other methane bands, was applied to all the transitions included in the fitted region. The present measurements are compared to values reported in the literature.

The accuracy of atmospheric trace gas retrievals depends directly on the accuracy of the molecular absorption model used within the retrieval algorithm. For remote sensing of well-mixed gases, such as carbon dioxide (CO 2 ), where the atmospheric variability is small compared to the background, the quality of the molecular absorption model is key. Recent updates to the 1.6 µm and 2.06 µm CO 2 absorption model used within the Orbiting Carbon Observatory (OCO-2) algorithm are described and validated. A set of 164 atmospheric spectra from the Total Carbon Column Observing Network (TCCON) is used to compare three models, both previous and current versions of absorption coefficient tables (largely derived from recent multispectrum fitting analyses targeted specifically at these bands) as well as a recent model constructed to use the HITRAN 2012 compilation. Both spectral residuals and retrieved column-averaged CO 2 mixing ratios (XCO 2 ) are included in the comparison. Absorption coefficients based on the updated multispectrum fitting analyses provide residuals comparable to or smaller than either the previous version of the multispectrum fits or the HITRAN 2012-based model. For the 2.06 µm band the updated model finds noticeably lower residuals for low water content cases. It is found that apart from a scaling factor the prior and updated absorption models result in similar retrieved values of XCO 2 for the 2.06 µm band and a slightly different airmass dependence for the 1.6 µm band.

CO 2 -rich planetary atmospheres such as those of Mars and Venus require accurate knowledge of CO 2 broadened HDO half-width coefficients and their temperature dependence exponents for reliable abundance determination. Although a few calculated line lists have recently been published on HDO–CO 2 line shapes and their temperature dependences, laboratory measurements of those parameters are thus far non-existent. In this work, we report the first measurements of CO 2 -broadened half-width and pressure-shift coefficients and their temperature dependences for over 220 transitions in the ν 2 band. First measurements of self-broadened half-width and self-shift coefficients at room temperature are also obtained for majority of these transitions. In addition, the first experimental determination of collisional line mixing has been reported for 11 transition pairs for HDO–CO 2 and HDO–HDO systems. These results were obtained by analyzing ten high-resolution spectra of HDO and HDO–CO 2 mixtures at various sample temperatures and pressures recorded with the Bruker IFS-125HR Fourier transform spectrometer at the Jet Propulsion Laboratory (JPL). Two coolable absorption cells with path lengths of 20.38 cm and 20.941 m were used to record the spectra. The various line parameters were retrieved by fitting all ten spectra simultaneously using a multispectrum nonlinear least squares fitting algorithm. The HDO transitions in the 1100–4100 cm −1 range were extracted from the HITRAN2012 database. For the ν 2 and 2ν 2 -ν 2 bands there were 2245 and 435 transitions, respectively. Modified Complex Robert–Bonamy formalism (MCRB) calculations were made for the half-width coefficients, their temperature dependence and the pressure shift coefficients for the HDO–CO 2 and HDO–HDO collision systems. MCRB calculations are compared with the measured values.

Due to the importance of methane as a trace atmospheric gas and a greenhouse gas, we have carried out a precise line-shape study to obtain the CH 4 –CH 4 and CH 4 –air half-width coefficients, CH 4 –CH 4 and CH 4 –air shift coefficients and off-diagonal relaxation matrix element coefficients for methane transitions in the spectral range known as the “ methane Octad ”. In addition, the associated temperature dependences of these coefficients have been measured in the 4300–4500 cm −1 region of the Octad. The high signal to noise ratio spectra of pure methane and of dilute mixtures of methane in dry air with high resolution have been recorded at temperatures from 148 K to room temperature using the Bruker IFS 125 HR Fourier transform spectrometer (FTS) at the Jet Propulsion Laboratory, Pasadena, California. The analysis of spectra was done using a multispectrum non-linear least-squares curve fitting technique. Theoretical calculations have been performed and the results are compared with the previously published line positions, intensities and with the line parameters available in the GEISA and HITRAN2012 databases.

This study reports the results from analyzing a number of high resolution, high signal-to-noise ratio (S/N) spectra in the 2.06-μm spectral region for pure CO2 and mixtures of CO2 in dry air. A multispectrum nonlinear least squares curve fitting technique has been used to retrieve the various spectral line parameters. The dataset includes 27 spectra: ten pure CO2, two 99% 13C-enriched CO2 and fifteen spectra of mixtures of 12C-enriched CO2 in dry air. The spectra were recorded at various gas sample temperatures between 170 and 297 K. The absorption path lengths range from 0.347 to 49 m. The sample pressures for the pure CO2 spectra varied from 1.1 to 594 Torr; for the two 13CO2 spectra the pressures were ∼10 and 146 Torr. For the air-broadened spectra, the pressures of the gas mixtures varied between 200 and 711 Torr with CO2 volume mixing ratios ranging from 0.014% to 0.203%. The multispectrum fitting technique was applied to fit simultaneously all these spectra to retrieve consistent set of line positions, intensities, and line shape parameters including their temperature dependences; for this, the Voigt line shape was modified to include line mixing (via the relaxation matrix formalism) and quadratic speed dependence. The new results are compared to select published values, including recent ab initio calculations. These results are required to retrieve the column averaged dry air mole fraction (XCO2) from space-based observations, such as the Orbiting Carbon Observatory-2 (OCO-2) satellite mission that NASA launched in July 2014.

Pressure-broadened line shapes in the 30013←00001 (ν1+4 ν 2 0 +ν3) band of 12C16O2 at 6228 cm−1 are reanalyzed using new spectra recorded with sample temperatures down to 170 K. High resolution, high signal-to-noise (S/N) laboratory measurements of line shapes (Lorentz air- and self-broadened half-width coefficients, pressure-shift coefficients and off-diagonal relaxation matrix element coefficients) as a function of gas sample temperatures for various pressures and volume mixing ratios are presented. The spectra were recorded using two different Fourier transform spectrometers (FTS): (1) the McMath-Pierce FTS located at the National Solar Observatory on Kitt Peak, Arizona (and reported in Devi et al., J Mol Spectrosc 2007;245:52-80) and, (2) the Bruker IFS-125HR FTS at the Jet Propulsion Laboratory in Pasadena, California. The 19 spectra taken at Kitt Peak were all recorded near room temperature while the 27 Bruker spectra were acquired both at room temperature and colder temperatures (170-296 K). Various spectral resolutions (0.004–0.011 cm−1), absorption path lengths (2.46–121 m) and CO2 samples (natural and 12C-enriched) were included in the dataset. To maximize the accuracies of the various retrieved line parameters, a multispectrum nonlinear least squares spectrum fitting software program was used to adjust the ro-vibrational constants (G,B,D etc.) and intensity parameters (including Herman-Wallis terms) instead of directly measuring the individual line positions and intensities. To minimize systematic residuals, line mixing (via off-diagonal relaxation matrix elements) and quadratic speed dependence parameters were included in the analysis. Contributions from other weakly absorbing bands: the 30013←00001 and 30012←00001 bands of 13C16O2, the 30013←00001 band of 12C16O18O, hot bands 31113←01101 and 32212←02201 of 12C16O2, as well as the 40013←10001 and the 40014←10002 bands of 12C16O2, present within the fitted interval were also measured. Results from previous works and new calculations are compared to present measurements, where appropriate.

In this study, we report the first experimental measurements of spectral line shape parameters (self- and air-broadened Lorentz half-widths, pressure-shifts, and line mixing (via off-diagonal relaxation matrix elements) coefficients and their temperature dependences, where appropriate) for transitions in the 2ν 3 Q branch manifolds, Q(11)–Q(1) of methane ( 12 CH 4 ), in the 5996.5–6007-cm −1 region. The analysis included 23 high-resolution, high signal-to-noise laboratory absorption spectra recorded with the Bruker IFS-125HR Fourier transform spectrometer (FTS) at JPL. The experimental data were obtained using 12 C-enriched 12 CH 4 and dilute mixtures of 12 CH 4 in dry air in the 130–296 K range using a room-temperature long path absorption cell and, two custom-built coolable cells. In the analysis, an interactive multispectrum fitting software was employed where all the 23 spectra (11 self-broadened and 12 air-broadened) were fit simultaneously. By carefully applying reasonable constraints to the parameters for severely blended lines, we were able to determine a self-consistent set of broadening, shift and line mixing (relaxation matrix coefficients) parameters for CH 4 –CH 4 and CH 4 –air collisions. In the majority of cases, a quadratic speed dependence parameter common for all transitions in each Q( J ) manifold was determined. However, temperature dependences of the Q branch line mixing parameter could not be determined from the present data. Since no other experimental line shape measurements have been reported for this Q-branch, the present results are compared to available values in the HITRAN2012 database.

We have made the measurements of H2-broadened line shape parameters of CH4 transitions in the v2+v3 band located at 2.2 µm. These measurements support atmospheric opacity calculations of cold giant planets, hot Jupiters, and low mass brown dwarfs, for which H2 is the dominant atmospheric constituent. For this reason, a series of spectra of pure CH4 and CH4 H2 mixtures were obtained in the Octad (4100–4600 cm−1) region for a wide temperature range between 80 and 370 K using a Bruker 125HR high-resolution Fourier transform spectrometer (FTS) at Jet Propulsion Laboratory (JPL). Three custom-designed gas absorption cells vacuum-coupled to the FTS were used to obtain the spectra. All spectra were fit simultaneously using a multispectrum non-linear least-squares fitting software, which adopts a speed-dependent Voigt line shape using full line mixing taken into account through a relaxation matrix operation. H2 pressure broadened half-widths, and H2 pressure-induced shift coefficients were determined in 11 J-manifolds covering P(4) – R(6) plus the Q-branch. The temperature dependences of the width and shift coefficients were determined based upon the power law and the linear models. Collisional line mixing coefficients for CH4 H2 were retrieved for ten transition pairs. For the same transitions, speed dependence parameters for the CH4 H2 transitions were found to be smaller than for CH4-air-broadening. We have compiled the retrieved line parameters in an electronic format and reported as supplemental document. This will facilitate the analyses of planetary and exoplanetary atmospheres using ground-, air- and space-based observations (e.g., Keck I and II, SOFIA, JWST).

In this paper we report line shape parameters of 12 CH 4 for several hundred 2ν 3 transitions in the spectral regions 5891–5996 cm −1 (P branch) and 6015–6115 cm −1 (R branch). Air- and self-broadening coefficients were measured as a function of temperature; line mixing via off-diagonal relaxation matrix element coefficients was also obtained for 47 transition pairs. In total, nearly 1517 positions and intensities were retrieved, but many transitions were too weak for the line shape study. For this analysis, we used 25 high-resolution (0.0056 and 0.0067 cm −1 ) and high signal-to-noise (S/N) spectra of high-purity 12 CH 4 and the same high-purity 12 CH 4 broadened by dry air recorded at different sample temperatures between 130 K and 295 K with the Bruker IFS 125HR Fourier transform spectrometer at JPL. Three different absorption cells were used (1) a White cell set to a path length of 13.09 m for room temperature data, (2) a single-pass 0.2038 m long coolable cell (for self-broadening) and (3) a multipass cell with 20.941 m total path coolable Herriott cell (for air-broadening). In total there were 13 spectra with pure 12 CH 4 (0.27–599 Torr) and 12 air-broadened spectra with total sample pressures of 80–805 Torr and volume mixing ratios (VMR) of methane between 0.18 and 1.0. An interactive multispectrum nonlinear least-squares technique was employed to fit the individual P10–P1 and R0–R10 manifolds in all the spectra simultaneously. Results obtained from the present analysis are compared to other recent measurements.

Accurate knowledge of spectral line shape parameters is important for infrared transmission and radiance calculations in the terrestrial atmosphere. In this paper, we report the self- and air-broadened Lorentz half-widths, pressure-induced shifts and line mixing coefficients (via off-diagonal relaxation matrix elements) along with their temperature dependences for methane ν2+ν3 absorption lines in the 4500–4630 cm−1 region of the Octad. For this, we recorded 14 high-resolution, high signal to noise ratio (S/N) spectra of high-purity (99.95% 12C-enriched) samples of pure methane and its dilute mixtures in dry air between 298 K and 148 K. A Bruker IFS 125HR Fourier transform spectrometer (FTS) at the Jet Propulsion Laboratory, Pasadena, California, was used to obtain the experimental data. The absorption cell used for this study was a specially built 20.38 cm long coolable cell installed in its sample compartment. The sample pressures for the pure 12CH4 spectra were 4.5−385 Torr; for the air-broadened spectra the total pressures ranged between 95 and 300 Torr with the methane volume mixing ratios between 0.04 and 0.097. All 14 spectra were fitted simultaneously using an interactive multispectrum nonlinear least-squares curve fitting technique. The results are compared to values reported in the literature.

Accurate knowledge of spectroscopic line parameters of PH3 is important for remote sensing of the outer planets, especially Jupiter and Saturn. In a recent study, line positions and intensities for the Pentad bands of PH3 have been reported from analysis of high-resolution, high signal-to noise room-temperature spectra recorded with two Fourier transform spectrometers (2014) [1]. The results presented in this study were obtained during the analysis of positions and intensities, but here we focus on the measurements of spectral line shapes (e.g. widths, shifts, line mixing) for the 2ν4, ν2 + ν4, ν1 and ν3 bands. A multispectrum nonlinear least squares curve fitting technique employing a non-Voigt line shape to include line mixing and speed dependence of the Lorentz width was employed to fit the spectra simultaneously. The least squares fittings were performed on five room-temperature spectra recorded at various PH3 pressures (∼2-50 Torr) with the Bruker IFS-125HR Fourier transform spectrometer (FTS) located at the Pacific Northwest National Laboratory (PNNL), in Richland, Washington. Over 840 Lorentz self-broadened half-width coefficients, 620 self-shift coefficients and 185 speed dependence parameters were measured. Line mixing was detected for transitions in the 2ν4, ν1 and ν3 bands, and their values were quantified for 10 A+A- pairs of transitions via off-diagonal relaxation matrix element formalism. The dependences of the measured half-width coefficients on the J and K rotational quanta of the transitions are discussed. The self-width coefficients for the ν1 and ν3 bands from this study are compared to the self-width coefficients for transitions with the same rotational quanta (J, K) reported for the Dyad (ν2 and ν4) bands. The measurements from present study should be useful for the development of a reliable theoretical modeling of pressure-broadened widths, shifts and line mixing in symmetric top molecules with C3v symmetry in general, and of PH3 in particular. © 2014 Elsevier Inc. All rights reserved.

In order to improve the spectroscopic database for remote sensing of the giant planets, line positions and intensities are determined for the five bands (2ν 2 , ν 2 + ν 4 , 2ν 4 , ν 1 and ν 3 ) that comprise the Pentad of PH 3 between 1950 and 2450 cm −1 . Knowledge of PH 3 spectral line parameters in this region is important for the exploration of dynamics and chemistry on Saturn, (using existing Cassini/VIMS observations) and future near-IR data of Jupiter from Juno and ESA’s Jupiter Icy Moons Explorer (JUICE). For this study, spectra of pure PH 3 from two Fourier transform spectrometers were obtained: (a) five high-resolution (0.00223 cm −1 ), high signal-to-noise (∼1800) spectra recorded at room temperature (298.2 K) with the Bruker IFS 125HR Fourier transform spectrometer (FTS) at the Pacific Northwest National Laboratory (PNNL), Richland, Washington and (b) four high-resolution (at 0.0115 cm −1 resolution), high signal-to-noise (∼700) spectra recorded at room temperature in the region 1800–5200 cm −1 using the McMath-Pierce Fourier transform spectrometer located at the National Solar Observatory (NSO) on Kitt Peak. Individual line parameters above 2150 cm −1 were retrieved by simultaneous multispectrum fittings of all five Bruker spectra, while retrievals with the four Kitt Peak spectra were done in the 1938–2168 cm −1 range spectrum by spectrum and averaged. In all, positions and intensities were obtained for more than 4400 lines. These included 53 A+A− split pairs of transitions (arising due to vibration–rotation interactions (Coriolis-type interaction) between the ν 3 and ν 1 fundamental bands) for K ″ = 3, 6, and 9. Over 3400 positions and 1750 intensities of these lines were ultimately identified as relatively unblended and modeled up to J = 14 and K = 12 with rms values of 0.00133 cm −1 and 7.7%, respectively. The PH 3 line parameters (observed positions and measured intensities with known quantum assignments) and Hamiltonian constants are reported. Comparisons with other recent studies are discussed.

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.

Temperature dependences of pressure-broadened half-width and pressure-induced shift coefficients along with accurate positions and intensities have been determined for transitions in the 2←0 band of 12C16O from analyzing high-resolution and high signal-to-noise spectra recorded with two different Fourier transform spectrometers. A total of 28 spectra, 16 self-broadened and 12 air-broadened, recorded using high-purity (≥99.5% 12C-enriched) CO samples and CO diluted with dry air (research grade) at different temperatures and pressures, were analyzed simultaneously to maximize the accuracy of the retrieved parameters. The sample temperatures ranged from 150 to 298 K and the total pressures varied between 5 and 700 Torr. A multispectrum nonlinear least squares spectrum fitting technique was used to adjust the rovibrational constants (G, B, D, etc.) and intensity parameters (including Herman–Wallis coefficients), rather than determining individual line positions and intensities. Self- and air-broadened Lorentz half-width coefficients, their temperature dependence exponents, self- and air-pressure-induced shift coefficients, their temperature dependences, self- and air- line mixing coefficients, their temperature dependences and speed dependence have been retrieved from the analysis. Speed-dependent line shapes with line mixing employing off-diagonal relaxation matrix element formalism were needed to minimize the fit residuals. This study presents a precise and complete set of spectral line parameters that consistently reproduce the spectrum of carbon monoxide over terrestrial atmospheric conditions.

The first air broadening line shape parameters were determined for the 2 ← 0 bands of 13C16O near 4166.8 cm−1 and 12C18O near 4159.0 cm−1. Air-broadened Lorentz half-width coefficients, their temperature dependence exponents; air-induced pressure shift coefficients, their temperature dependences; and air line mixing coefficients were measured. Additionally, speed-dependent line shapes with line mixing employing the off-diagonal relaxation matrix element coefficients were applied to minimize the fit residuals. Finally, individual line positions and line intensities of the two isotopologues were constrained to the well-known theoretical quantum mechanical expressions in order to obtain the rovibrational (G, B, D and H) and band intensity parameters (including Herman–Wallis coefficients). For this, laboratory spectra were recorded at 0.005 cm−1 resolution using a temperature-controlled coolable absorption cell configured inside a Bruker IFS 125HR Fourier transform spectrometer. Gas temperatures and pressures for the spectra varied from 150 to 298 K and 20 to 700 Torr, respectively. Results were obtained from broad-band multispectrum least-squares fitting of the 4000–4360 cm−1 spectral region. Four isotope-enriched pure sample spectra and twelve spectra with air + CO samples (13C16O or 12C18O, as appropriate) were fitted simultaneously. The results obtained for 13C16O and 12C18O are compared and discussed.

Line positions, Lorentz air-broadened half width and air pressure-induced shift coefficients have been measured for nearly 200 transitions in the ν 4 band of 13 CH 4 from high-resolution spectra recorded with the McMath-Pierce Fourier transform spectrometer. Three room temperature spectra of 13 CH 4 used in the previous study of Malathy Devi et al. (Air-broadened Lorentz halfwidths and pressure-induced line shifts in the ν 4 band of 13 CH 4 . Appl. Opt. 1988; 27: 2296–2308) were analyzed together with a large number of additional spectra of self- and air-broadened CH 4 recorded at 210–314 K and one room-temperature spectrum of self-broadened 13 CH 4 . Analyses applying the multispectrum nonlinear least squares fitting technique were performed to retrieve the spectral line parameters. In addition to air-broadened half width and shift coefficients, self-broadened half width and shift coefficients were determined for at least 56 13 CH 4 ν 4 transitions. Off-diagonal relaxation matrix element coefficients for air-broadened line mixing were also determined for 28 pairs of P and R transitions in a number of J manifolds, and mixing parameters for self-broadening were also determined for some of these pairs. Temperature-dependences of the pressure-induced shift and mixing parameters for the 13 CH 4 lines could not be determined from the spectra used in the present analysis, but temperature dependences of the half width coefficients were determined for the strongest transitions. The results of this study are compared with other studies of air- and self-broadened 13 CH 4 and 12 CH 4 .

The McMath-Pierce Fourier transform spectrometer located at the National Solar Observatory (NSO) on Kitt Peak, Arizona, was used to record infrared high resolution absorption spectra of CO 2 spectra broadened by O 2 . These spectra were analyzed to measure O 2 -broadened half-width coefficients, O 2 -induced pressure-shift coefficients and speed dependent parameters for transitions in the 30013←00001 and 30012←00001 bands of 16 O 12 C 16 O located near 6227 and 6348 cm −1 , respectively. All spectra were obtained at room temperature using the long path, 6 m base path White cell available at NSO. A multispectrum nonlinear least-squares fitting algorithm employing Voigt line shapes modified to include line mixing and speed dependence was used to fit simultaneously a total of 19 spectra in the 6120–6280 cm −1 (30013←00001) and 6280–6395 cm −1 (30012←00001) spectral regions. 16 of the 19 spectra analyzed in this work were self broadened and three spectra were lean mixtures of CO 2 in O 2 . The volume mixing ratios of CO 2 in the three spectra varied between 0.06 and 0.1. Lorentz half-width and pressure-induced shift coefficients were measured for all transitions in the P(50)–R(50) range in both vibrational bands. The results obtained from present analysis have been compared with measurements available in the literature for self-, air-, oxygen- and argon-broadening. No significant differences were observed between the broadening and shift coefficients of the two bands. The N 2 -broadened half-width and pressure-shift coefficients were computed from measured air- and O 2 -broadened width and shift coefficients.

Ethane is a prominent contributor to the spectrum of Titan, particularly in the ν 9 region centered near 822 cm −1 . To improve the spectroscopic line parameters at 12 μm, 41 high-resolution (0.0016–0.005 cm −1 ) absorption spectra of C 2 H 6 were obtained at sample temperatures between 211 and 298 K with the Bruker IFS 120HR at the Pacific Northwest National Laboratory (PNNL) in Richland, Washington. Two additional spectra were later recorded at ∼150 K using a new temperature-stabilized cryogenic cell designed for the sample compartment of the Bruker IFS 125HR at the Jet Propulsion Laboratory (JPL) in Pasadena, California. A multispectrum nonlinear least-squares fitting program was applied simultaneously to all 43 spectra to measure the line positions, intensities, N 2 - and self-broadened half-width coefficients and their temperature dependences. Reliable pressure-induced shift coefficients could not be obtained, however, because of the high congestion of spectral lines (due to torsional-split components, hot-band transitions as well as blends). Existing theoretical modeling of this very complicated ν 9 region permitted effective control of the multispectrum fitting technique; some constraints were applied using predicted intensity ratios, doublet separations, half-width coefficients and their temperature dependence exponents in order to determine reliable parameters for each of the two torsional-split components. For 12 C 2 H 6 , the resulting retrievals included 17 p Q and r Q sub-bands of ν 9 (as well as some p P, r R sub-bands). Positions and intensities were measured for 3771 transitions, and a puzzling difference between previously measured ν 9 intensities was clarified. In addition, line positions and intensities were obtained for two 12 C 2 H 6 hot bands (ν 9 +ν 4 −ν 4 , ν 9 +2ν 4 −2ν 4 ) and the ν 9 band of 13 C 12 CH 6 , as well as several hundred presently unidentified transitions. N 2 - and self-broadened half-width coefficients were determined for over 1700 transitions, along with 1350 corresponding temperature dependence exponents. Similar to N 2 - and self-broadened half-width coefficients, their temperature dependence exponents were also found to follow distinctively different patterns. However, while the self- and N 2 -broaded widths differed by 40%, the temperature dependence exponents of the two broadening gases were similar. The variations of the observed half-width coefficients and their temperature dependences with respect to J , K quantum numbers were modeled with a set of linear equations for each K . The present broadening coefficients compared well with some of the prior measurements.

Line positions, intensities, Lorentz self- and N2-broadened half-width coefficients have been measured for PQ3, PQ2, PQ1, RQ0, RQ1, RQ2, and RQ3 sub-band transitions in the ν9 fundamental band of 12C2H6. A multispectrum nonlinear least-squares fitting technique was used to fit up to 17 high-resolution (∼0.00156 cm−1), room temperature absorption spectra of pure (99.99% chemical purity) natural sample of ethane and lean mixtures of the high-purity ethane diluted with N2. A Bruker IFS 120HR Fourier transform spectrometer located at the Pacific Northwest National Laboratory (PNNL), in Richland, Washington was used to record the data. A standard Voigt line shape was assumed to fit all the data since no line mixing or other non Voigt line shapes were required to fit any of the spectra used in the analysis. Short spectral intervals (∼2–2.5 cm−1) of all 17 spectra covering a specific PQ or RQ sub-band were fit simultaneously. For the first time in an ethane band, pressure-broadened half-width coefficients were determined for the torsional-split components. However, for better reliability of the retrieved coefficients for the weaker components (transitions with large intensity ratios of 4:1 or 3:1 for most K levels between the strong and weak components), constraints were used such that the half-width coefficients of both torsional-split components for a given J were identical for a specific broadening gas. No pressure-induced shift coefficients were necessary to fit the spectra to their noise level. The present study revealed for the first time the dependence of self- and N2-broadened half-width coefficients upon the J, K quantum numbers of the transitions in ethane. A number of transitions belonging to the ν9+ν4−ν4 and the ν9+2ν4−2ν4 hot bands were also observed in the fitted regions and measurements were made when possible.

Accurate values for line positions, absolute line intensities, self-broadened half width and self-pressure-induced shift coefficients have been measured for over 400 allowed and forbidden transitions in the ν4 band of methane (12CH4). Temperature dependences of half width and pressure-induced shift coefficients were also determined for many of these transitions. The spectra used in this study were recorded at temperatures between 210 and 314 K using the National Solar Observatory's 1 m Fourier transform spectrometer at the McMath-Pierce solar telescope. The complete data set included 60 high-resolution (0.006–0.01 cm−1) absorption spectra of pure methane and methane mixed with dry air. The analysis was performed using a multispectrum nonlinear least squares curve fitting technique where a number of spectra (20 or more) were fit simultaneously in spectral intervals 5–15 cm−1 wide. In addition to the line broadening and shift parameters, line mixing coefficients (using the off-diagonal relaxation matrix element formalism) were determined for more than 50 A-, E-, and F-species transition pairs in J manifolds of the P- and R-branches. The measured self-broadened half width and self-shift coefficients, their temperature dependences and the line mixing parameters are compared to self-broadening results available in the literature and to air-broadened parameters determined for these transitions from the same set of spectra.

Using a Fourier transform spectrometer setup we have measured the self-broadened half width, pressure shift, and line asymmetry coefficients for transitions in the 30012’00001 and 30013’00001 vibrational bands of carbon dioxide for four different temperatures. A total of 46 pure CO2 spectra were recorded at 0.008 and 0.009 cm � 1 resolution and at pressures varying from a few Torr to nearly an atmosphere. The individual spectral line profiles have been fitted by a Voigt profile and a speeddependent Voigt profile, to which we have added dispersion profiles to account for weak line mixing. A comparison of the sets of results obtained for each band showed no vibrational dependence of the broadening coefficients. The self-broadening and selfshift coefficients are compared to semiclassical calculations based on the Robert– Bonamy formalism and were found to be in good agreement. The line asymmetry results are compared to line mixing calculations based on the Energy Corrected Sudden (ECS) and Exponential Power Gap models.

Lorentz air-broadened half widths, pressure-induced shifts and their temperature dependences have been measured for over 430 transitions (allowed and forbidden) in the v4 band of (CH4)-12 over the temperature range 210 to 314 K. A multispectrum non linear least squares fitting technique was used to simultaneously fit a large number of high-resolution (0.006 to 0.01/cm) absorption spectra of pure methane and mixtures of methane diluted with dry air. Line mixing was detected for pairs of A-, E-, and F-species transitions in the P- and R-branch manifolds and quantified using the off-diagonal relaxation matrix elements formalism. The measured parameters are compared to air- and N2-broadened values reported in the literature for the v4 and other bands. The dependence of the various spectral line parameters upon the tetrahedral symmetry species and rotational quantum numbers of the transitions is discussed. All data used in the present work were recorded using the McMath-Pierce Fourier transform spectrometer located at the National Solar Observatory on Kitt Peak.

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.

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.

Pressure broadened (1 atm. N2) laboratory spectra of benzene vapor (in natural abundance) were recorded at 278, 298, and 323 K, covering 600–6500 cm−1. The spectra were recorded at a resolution of 0.112 cm−1 using a commercial Fourier transform spectrometer. The pressure of each benzene vapor sample was measured using high-precision capacitance manometers, and a minimum of nine sample pressures were recorded for each temperature. The samples were introduced into a temperature-stabilized static cell (19.94(1) cm pathlength) that was hard-mounted into the spectrometer. From these data a fit composite spectrum was calculated for each temperature. The number density for the three composite spectra was normalized to 296 K. The spectra give the absorption coefficient (cm2 molecule−1, naperian units) as a function of wavenumber. From these spectra integrated band intensities (cm molecule−1 and atm−1 cm−2) for intervals corresponding to the stronger benzene bands were calculated and were compared with previously reported values. We discuss and quantify error sources and estimate our systematic (NIST Type-B) errors to be 3% for the stronger bands. The measured absorption coefficients and integrated band intensities are useful for remote sensing applications such as measurements of planetary atmospheres and assessment of the environmental impact of terrestrial oil fire emissions.

Half-width and pressure-induced shift coefficients; the temperature-dependence exponents of the half-widths and the temperature-dependence coefficients of pressure-induced shifts have been measured for N2-broadened transitions in the ν2 band of HCN. Line positions and intensities were also determined. A total of 34 laboratory absorption spectra, recorded at 0.002–0.005 cm−1 resolution with two different Fourier transform spectrometers, were used in the determination of the spectral line parameters. The total pressures of the HCN–N2 samples ranged from less than 1 torr up to nearly 1 atm, and temperatures were between 211 and 300 K. A multispectrum nonlinear least-squares fitting technique employing a modified Voigt line profile, including speed dependence and line mixing via the off-diagonal relaxation matrix formulation, was used in the analysis. Speed-dependence parameters were determined in the P and R branches of the ν2 band of H12C14N, and in the ν2 Q branches of H12C14N and H13C14N the off-diagonal relaxation matrix elements that characterize line mixing were included in the analysis to fit the data. Present results are compared with previous measurements reported in the literature.

This study provides the first direct experimental measurements of the off-diagonal relaxation matrix element coefficients for line mixing in air-broadened methane spectra for any vibrational band and the first off diagonal relaxation matrix elements associated with line mixing for pure methane in the ν 2 + ν 3 band of 12 CH 4 . The speed-dependent Voigt profile with line mixing is used with a multispectrum nonlinear least squares curve fitting technique to retrieve the various line parameters from 11 self-broadened and 10 air-broadened spectra simultaneously. The room temperature spectra analyzed in this work are recorded at 0.011 cm −1 resolution with the McMath-Pierce Fourier transform spectrometer located at the National Solar Observatory, Kitt Peak, Arizona. The off-diagonal relaxation matrix element coefficients of ν 2 + ν 3 transitions between 4410 and 4629 cm −1 are reported for eighteen pairs with upper state J values between 2 and 11. The observed line mixing coefficients for self broadening vary from 0.0019 to 0.0390 cm −1 atm −1 at 296 K. The measured line mixing coefficients for air broadening vary from 0.0005 to 0.0205 cm −1 atm −1 at 296 K.

Line position, intensity and line shape parameters (Lorentz widths, pressure shifts, line mixing, speed dependence) are reported for transitions of the 30013 ← 00001 band of 16O12C16O (ν0 = 6227.9 cm−1). The results are determined from 26 high-resolution, high signal-to-noise ratio spectra recorded at room temperature with the McMath-Pierce Fourier transform spectrometer. To minimize the systematic errors of the retrieved parameters, we constrained the multispectrum nonlinear least squares retrieval technique to use quantum mechanical expressions for the rovibrational energies and intensities rather than retrieving the individual positions and intensities line by line. Self- and air-broadened Lorentz width and pressure-induced shift, speed dependence and line mixing (off-diagonal relaxation matrix elements) coefficients were adjusted individually. Errors were further reduced by simultaneously fitting the interfering absorptions from the weak 30012 ← 00001 band of 16O13C16O as well as the weak hot bands 31113 ← 01101, 32213 ← 02201, 40014 ← 10002 and 40013 ← 10001 of 16O12C16O in this spectral window. This study complements our previous work on line mixing and speed dependence in the 30012 ← 00001 band (ν0 = 6347.8 cm−1) [V.M. Devi, D.C. Benner, L.R. Brown, C.E. Miller, R.A. Toth, J. Mol. Spectrosc. 242 (2007) 90-117] and provides key data needed to improve atmospheric remote sensing of CO2.

Intensity and line shape parameters which predict spectral lines with absolute accuracies better than 0.3% have been determined for transitions of the 30012 ← 00001 band of 16 O 12 C 16 O centered near 6348 cm −1 from 26 high resolution, high signal-to-noise ratio spectra recorded at room temperature with the McMath–Pierce Fourier transform spectrometer. To maximize the accuracies of the retrieved parameters, the multispectrum non-linear least squares retrieval technique was modified to adjust the rovibrational constants ( G , B , D , etc.) and intensity parameters, including Herman–Wallis terms, rather than retrieving the individual positions and intensities. Speed-dependent Voigt line shapes with line mixing were required to remove systematic errors in the fit residuals. Self- and air-broadening (widths and pressure-induced shifts, speed dependence parameters) and line mixing (off-diagonal relaxation matrix elements) coefficients were thus obtained in the multispectrum fit. Remaining errors were minimized by fitting the weak 30011 ← 00001 band of 16 O 13 C 16 O as well as the weak hot bands 31112 ← 01101, 32212 ← 02201, 40012 ← 10001, and 40013 ← 10002 of 16 O 12 C 16 O that contribute interfering absorptions in this spectral window. This study presents the most extensive set of measurements to date for self- and air-broadening and self- and air-shift coefficients of a near infrared band of CO 2 . This is also the first study where line mixing parameters have been experimentally determined for any parallel CO 2 band.

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.

Line positions and strengths of 12 C 16 O 2 were measured between 4550 and 7000 cm −1 using near infrared absorption spectra recorded at 0.01–0.013 cm −1 resolution with the McMath-Pierce Fourier transform spectrometer located at the National Solar Observatory at Kitt Peak, Arizona. These were retrieved from 42 laboratory spectra obtained at room temperature with five absorption cells having various optical path lengths (from 0.1 to 409 m) filled with natural and enriched samples of CO 2 at pressures ranging from 2 to 581 Torr. In all, band strengths and Herman–Wallis-like F -factor coefficients were determined for 58 vibration–rotation bands from the least-squares fits of over 2100 unblended line strengths; strengths of 34 of these bands had not been previously reported. Band strengths in natural abundance generally ranged from 3.30 × 10 −20 to 2.8 × 10 −25 cm −1 /molecule cm −2 at 296 K. It was found that the high J transitions ( J ′ ⩾ 61) of the 20012 ← 00001 band centered at 4977.8347 cm −1 are perturbed, affecting both measured positions and strengths. Two other interacting bands, 21113e ← 01101e and 40002e ← 01101e, were also analyzed using degenerate perturbation theory. Comparisons with corresponding values from the literature indicate that absolute accuracies better than 1% and precisions of 0.5% were achieved for the strongest bands.

The temperature dependence of air-broadened halfwidths are reported for some 500 transitions in the (000)-(000) and (010)-(000) bands of H2(16)O using gas sample temperatures ranging from 241 to 388 K. These observations were obtained from infrared laboratory spectra recorded at 0.006 to 0.011 cm(exp-1) resolution with the McMath-Pierce Fourier transform spectrometer located at Kitt Peak. The experimental values of the temperature dependence exponents, eta, were grouped into eight subsets and fitted to empirical functions in a semi-global procedure. Overall, the values of eta were found to decrease with increasing rotational quantum number J. The number of measurements (over 2200) and transitions (586) involved exceeds by a large margin that of any other comparable reported study.

We report measured Lorentz O2-broadening and O2-induced pressure-shift coefficients of CH3D in the nu(exp 2) fundamental band. Using a multispectrum fitting technique we have analyzed 11 laboratory absorption spectra recorded at 0.011 cm(exp 1) resolution using the McMath-Pierce Fourier transform spectrometer, Kitt Peak, Arizona. Two absorption cells with path lengths of 10.2 and 25 cm were used to record the spectra. The total sample pressures ranged from 0.98 to 339.85 Torr with CH3D volume mixing ratios of 0.012 in oxygen. We report measurements for O2 pressure-broadening coefficients of 320 nu(exp 2) transitions with quantum numbers as high as J0(sup w) = 17 and K = 14, where K(sup w) = K' is equivalent to K (for a parallel band). The measured O2-broadening coefficients range from 0.0153 to 0.0645 cm(exp -1) atm(exp -1) at 296 K. All the measured pressure-shifts are negative. The reported O2-induced pressure-shift coefficients vary from about -0.0017 to -0.0068 cm(exp -1) atm(exp -1). We have examined the dependence of the measured broadening and shift parameters on the J(sup W), and K quantum numbers and also developed empirical expressions to describe the broadening coefficients in terms of m (m = -J(sup W), J(sup W), and J(sup w) + 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%. The O2-broadening and pressure shift coefficients were calculated on the basis of a semiclassical model of interacting linear molecules performed by considering in addition to the electrostatic contributions the atom-atom Lennard-Jones potential. The theoretical results of the broadening coefficients are generally larger than the experimental data. Using for the trajectory model an isotropic Lennard-Jones potential derived from molecular parameters instead of the spherical average of the atom-atom model, a better agreement is obtained with these data, especially for |m

In this paper, we report measured Lorentz self-broadening and self-induced pressure-shift coefficients of 12CH3D in the ν2 fundamental band (ν0 ≈ 2200 cm−1). The multispectrum fitting technique allowed us to analyze simultaneously seven self-broadened absorption spectra. All spectra were recorded at the McMath-Pierce Fourier transform spectrometer of the National Solar Observatory (NSO) on Kitt Peak, AZ with an unapodized resolution of 0.0056 cm−1. Low-pressure (0.98–2.95 Torr) as well as high-pressure (17.5–303 Torr) spectra of 12C-enriched CH3D were recorded at room temperature to determine the pressure-broadening coefficients of 408 ν2 transitions with quantum numbers as high as J″ = 21 and K = 18, where K″ = K′ ≡ K (for a parallel band). The measured self-broadening coefficients range from 0.0349 to 0.0896 cm−1 atm−1 at 296 K. All the measured pressure-shifts are negative. The reported pressure-induced self-shift coefficients vary from about −0.004 to −0.008 cm−1 atm−1. 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 3.6%. A semiclassical theory based upon the Robert–Bonamy formalism of interacting linear molecules has been used to calculate these self-broadening and self-induced pressure-shift coefficients. In addition to the electrostatic interactions involving the octopole and hexadecapole moments of CH3D, the intermolecular potential includes also an atom–atom Lennard–Jones model. For low K (K ⩽ 3) with |m| ⩽ 8 the theoretical results of the broadening coefficients are in overall good agreement (3.0%) with the experimental data. For transitions with K approaching |m|, they are generally significantly underestimated (8.8%). The theoretical self-induced pressure shifts, whose vibrational contribution is derived from results in the QQ-branch, are generally smaller in magnitude than the experimental data in the QP-, and QR-branches (15.2%).

Room temperature Lorentz air-broadened halfwidth and pressure-induced air-shift coefficients were measured for 1011 transitions in the octad region of methane between 4100 and 4635 cm −1 . These measurements were made by analyzing 10 laboratory absorption spectra recorded at 0.011 cm −1 resolution using the McMath–Pierce Fourier transform spectrometer located at the National Solar Observatory on Kitt Peak, Arizona. The spectra were obtained using two absorption cells with path lengths of 2.05 and 150 cm. The total sample pressures ranged from 99 to 400 torr with CH 4 volume mixing ratios of 0.01 in dry air. The spectral line parameters were retrieved using a multispectrum nonlinear least squares technique. Transitions belonging to five bands of the octad polyad were observed, namely ν 2 + 2 ν 4 , ν 1 + ν 4 , ν 3 + ν 4 , 2 ν 2 + ν 4 , and ν 2 + ν 3 . The numbers of measurements by bands are: 33 for ν 2 + 2 ν 4 , 180 for ν 1 + ν 4 , 635 for ν 3 + ν 4 , 33 for 2 ν 2 + ν 4 , and 130 for ν 2 + ν 3 . Transitions with rotational quantum number J up to 16 are included in the analysis. The measured width and shift coefficients vary according to the tetrahedral symmetry species and the rotational quantum numbers of the transitions. The retrieved parameters from this study are compared with prior results, in part to estimate absolute accuracy and determine the extent of vibrational dependence of widths and shifts.

Lorentz pressure-broadening and pressure-induced shift coefficients along with their temperature dependences have been determined for over forty P- and R-branch transitions in the fundamental band of 12 C 16 O broadened with helium. A total of nineteen spectra recorded at various temperatures (+24 to −194 °C) in the 2010–2260 cm −1 spectral region were analyzed simultaneously using a multispectrum nonlinear least squares fitting technique. The spectra were recorded with the McMath-Pierce Fourier transform spectrometer located at the National Solar Observatory on Kitt Peak. Present results are compared with similar measurements reported recently.

Absolute intensities, self- and air-broadening coefficients, self- and air-induced shift coefficients and their temperature dependences have been determined for lines belonging to the P- and R-branches of the m2 band of H 12 C 14 N centered near 712 cm � 1 . Infrared spectra of HCN in the 14-lm region were obtained at high resolution (0.002–0.008 cm � 1 ) using two different Fourier transform spectrometers (FTS), the McMath-Pierce FTS at the National Solar Observatory on Kitt Peak and the Bruker IFS 120HR FTS at the Pacific Northwest National Laboratory. Spectra were recorded with 99.8% pure HCN as well as lean mixtures of HCN in air at various temperatures ranging between +26 and � 60 � C. A multispectrum nonlinear least squares technique was used to fit selected intervals of 36 spectra simultaneously to obtain the line positions, intensities, broadening, and shift parameters. The measured line intensities were analyzed to determine the vibrational band intensity and the Herman–Wallis coefficients. The measured self-broadening coefficients vary between 0.2 and 1.2 cm � 1 atm � 1 at 296 K, and the air-broadening coefficients range from 0.08 to 0.14 cm � 1 atm � 1 at 296 K. The temperature dependence exponents of self-broadening range from 1.46 to � 0.12 while the corresponding exponents for air broadening vary between 0.58 and 0.86. The present measurements are the first known determination of negative values for the temperature dependence exponents of HCN-broadening coefficients. We were able to support our selfbroadening measurements with appropriate theoretical calculations. Our present measurements are compared, where possible, with previous measurements for this and other HCN bands, as well as the parameters that are included in the 2000 and 2004 editions of the high-resolution transmission (HITRAN) database.

Air-broadened linewidths, pressure-induced shift coefficients and their temperature dependences were retrieved for over 1000 transitions in the ν 3 band of 14 N 16 O 2 at 6 μm. In addition, precise line center positions and relative intensities were also determined. The results were obtained by fitting simultaneously 27 spectra recorded at high resolution (0.002–0.006 cm −1 ) with two Fourier transform spectrometers and gas sample temperatures ranging from 206 to 298 K. It was necessary to modify the multispectrum fitting software to accommodate constraints on the retrieved parameters of closely spaced spin–split doublets in order to successfully determine their broadening and shift parameters. The variations of the widths, shifts and their temperature dependences with the quantum numbers were investigated. Subsets of the observed linewidths were reproduced to within 3% using an empirical smoothing function.

Room temperature values for self-broadened and hydrogen-broadened Lorentz halfwidth coefficients, and self and hydrogen pressure-induced shift coefficients have been measured for transitions with rotational quantum number m ranging between −24 and 24 in the 2 ← 0 band of 12 C 16 O. The spectra were recorded with the McMath–Pierce Fourier transform spectrometer located at the National Solar Observatory on Kitt Peak. The analysis was performed using a multispectrum nonlinear least squares technique. We have compared our results with similar measurements published recently.

High-resolution (0.005 cm −1 ) infrared absorption spectra of HCN in the 2ν2 band region near 1411 cm −1 have been recorded at room temperature using the Bruker IFS120HR Fourier transform spectrometer located at Pacific Northwest National Laboratory. Four spectra of high-purity (99.8%) HCN together with three spectra of lean mixtures (∼3%) of HCN in dry air were simultaneously fit using a multispectrum nonlinear least-squares procedure. The analysis yielded room temperature values for absolute intensities, self- and air-broadening coefficients, and self- and air-induced pressure shift coefficients for numerous lines in the 2ν20 band of H12C14N. In addition, intensities, self- and air-broadening coefficients for several lines of the 3ν21−ν21 hot band, as well as intensities for a number of lines in the 2ν20 band of H13C14N, were also determined. Since there are no previous measurements of broadening and shift parameters reported in the 2ν20 band, our results are compared with values recently determined in the ν1 band of H12C14N and with current HITRAN values.

Line intensities of the three lowest fundamentals of the 12CH3D Triad are modeled with an RMS of 3.2% using over 2100 observed values retrieved by multispectrum fitting of enriched sample spectra recorded with two Fourier transform spectrometers. The band strengths of the Triad in units of 10−18 cm−1/(molecule cm−2) at 296 K are, respectively, 2.33 for ν6 (E) at 1161 cm−1, 1.75 for ν3 (A1) at 1307 cm−1 and 0.571 for ν5 (E) at 1472 cm−1. The total calculated absorption arising from 12CH3D Triad fundamentals is 4.65×10−18 cm−1/(molecule cm−2) at 296 K. In addition, some 740 intensities of nine hotbands are fitted to 8.1%; most of the hotband measurements belong to 2ν6−ν6 and ν3+ν6−ν3 near 1160 cm−1, 2ν3−ν3 near 1290 cm−1 and ν3+ν6−ν6 near 1304 cm−1. The other observed hotbands are ν5+ν6−ν6, 2ν5−ν5, ν5+ν6−ν5, ν3+ν5−ν3, and ν3+ν5−ν5.

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.

Air- and N2-broadening, air- and N2-pressure-induced shift coefficients and the temperature dependence exponent of the broadening coefficients and the temperature dependent coefficient of pressure-induced shifts have been determined for transitions of the ν1 band of H12C14N from 39 laboratory absorption spectra recorded at 0.005 and 0.008 cm −1 resolutions with two different Fourier transform spectrometers. The parameters were retrieved from the multispectrum nonlinear least-squares fits to the 3200– 3400 cm −1 region of spectra recorded at temperatures between +26°C and −60°C. Pure samples of HCN in a 19.95 cell and a 0.958 cm cell at room temperature as well as lean mixtures of HCN in N2 or dry air in a coolable cell with a 50 cm absorption path were used in the experiments. Line parameters for N2 broadening were determined by fitting 27 spectra simultaneously while air-broadening parameters were quantified from simultaneous fits to 22 spectra. The average ratio and the standard deviation of the room-temperature air- to N2-broadening coefficient of lines with assignments between P(29) and R(28) are 0.904±0.001. Pressure-induced shift coefficients at 296 K are all negative with values between 0 and ∼−0.006 cm −1 atm −1 and different rotational dependences in the P- and R-branches. Differences between our results, previous measurements and the parameters that are reported in the 2000 edition of HITRAN (HIgh-resolution TRANsmission) database are quantified and discussed.