Line Shift Investigations for Different Isotopomers of Carbon Monoxide

Line shift coefficients for five lines of five different isotopomers in the fundamental band of CO in the spectral region near 2058 cm⁻¹were measured using a three channel lead salt diode laser spectrometer. The study includes the linesP(3) of¹³C¹⁷O,R(3) of¹³C¹⁸O,P(9) of¹²C¹⁸O,P(10) of¹³C¹⁶O, andP(21) of¹²C¹⁶O, and covers collisions with N₂, O₂, H₂, D₂, He, Ne, Ar, Kr, and Xe. Line shifts of the isotopomers¹³C¹⁶O,¹²C¹⁸O,¹³C¹⁸O, and¹³C¹⁷O were determined for the first time. Within the experimental uncertainty no significant dependence of the shift effect on the isotopomer was found. TheR-branch line under study shows a smaller line shift coefficient than aP-branch line with a similar rotational quantum number. With increasing mass of the noble gas perturber the absolute size of the shift coefficient increases. Moreover self- and nitrogen-broadening coefficients for the isotopomer lines were determined. Compared to previous measurements no significant deviations between different isotopomers were observed.     

Self-, N2- and O2-broadening coefficients for the CO2 transitions near-IR measured by a diode laser photoacoustic spectrometer

Using a high-resolution tunable diode laser photoacoustic spectrometer, self-, N₂ and O₂ pressure broadening coefficients for the first 11 transitions of ¹²C¹⁶O₂ in the R branch of the (30012) ← (00001) overtone band at the 6348 cm⁻¹ have been revisited at room temperature (∼298 K). Air-broadening parameters have also been calculated from the N₂ and O₂ measurements. The dependence of the broadening on rotational quantum number m is discussed. The recorded lineshapes are fitted with standard Voigt line profiles in order to determine the collisional broadening coefficients of carbon dioxide transitions. The results are compared to our previous measurements and to the values reported in the HITRAN04 database and by other research group with a different spectroscopic technique.     

The rotationally-resolved absorption spectrum of formaldehyde from 6547 to 6804 cm

The room temperature absorption spectrum of formaldehyde, H₂CO, from 6547 to 6804 cm⁻¹ (1527-1470 nm) is reported with a spectral resolution of 0.001 cm⁻¹. The spectrum was measured using cavity-enhanced absorption spectroscopy (CEAS) and absorption cross-sections were calculated after calibrating the system using known absorption lines of H₂O and CO₂. Several vibrational combination bands occur in this region and give rise to a congested spectrum with over 8000 lines observed. Pressure broadening coefficients in N₂, O₂, and H₂CO are reported for an absorption line at 6780.871 cm⁻¹, and in N₂ for an absorption line at 6684.053 cm⁻¹.     

Diode-laser measurements of O2, N2 and air-pressure broadening and shifting of NH3 in the 10 μm spectral region

Using a tunable diode-laser spectrometer, we have measured the O₂, N₂, air-shift and broadening coefficients for 5 lines of ammonia in the R branch of the ν₂ band. These lines are located in the spectral range 1030-1070 cm⁻¹. The pressure shift and broadening are obtained by fitting the measured shapes of these lines by a Voigt profile. The broadening parameters and shift coefficients are compared to the results of theoretical calculations based on the semiclassical Robert-Bonamy formalism (RB) in which the intermolecular potential includes electrostatic, induction, and dispersion energy contributions. The variation of these coefficients with rotational and vibrational quantum numbers is examined. The results are generally in satisfactory agreement with experimental data.     

Line broadening and shift coefficients of acetylene at 1550 nm

Pressure broadening and shift coefficients have been measured for the ν₁ + ν₃ band of acetylene, C₂H₂, broadened by N₂, H₂, D₂, air, and the noble gases at 295 K. Coefficients are reported for lines between 6470 and 6612 cm⁻¹ (1512-1546 nm). The pressure broadening coefficients are in general agreement with those reported for other vibrational bands, indicating that they are insensitive to vibrational excitation. The pressure shift coefficients, by contrast, are found to differ substantially among vibrational bands.     

Water absorption line, 931–961 nm: selected intensities,N2-collision-broadening coefficients,self-broadening coefficients,and pressure shifts in air

Intensities were measured for 97 lines of H₂O vapor between 932 and 961 nm. The lines were selected for their potential usefulness for remote laser measurements of H₂O vapor in the earth's atmosphere. The spectra were obtained with several different H₂O vapor abundances and N₂ broadening gas pressure; the spectral resolution was 0.046 cm^?1 FWHM. Measured H₂O line intensities range from 7 × 10^?25 to 7 × 10^?22 cm^?1/molecules/cm². H₂O self-broadening coefficients were measured for 13 of these strongest lines; the mean value was 0.5 cm^?1/atm. N₂-collision-broadening coefficients were measured for 73 lines, and the average was 0.11 cm^?1/atm HWHM. Pressure shifts in air were determined for a sample of six lines between 948 and 950 nm; these lines shift to lower frequency by an amount comparable to 0.1 of the collision-broadened widths measured in air or N₂. The measured intensities of mainly lines of the 300-000 band are much larger than expected from prior computations, in some cases by over ab order if magnitude. Coriolis interactions with the stronger 201-000 band appear to be the primary cause of the enhancement of these line intensities.     

Spectroscopic database of CO2 line parameters: 4300-7000 cm

A new spectroscopic database for carbon dioxide in the near infrared is presented to support remote sensing of the terrestrial planets (Mars, Venus and the Earth). The compilation contains over 28,500 transitions of 210 bands from 4300 to 7000 cm⁻¹ and involves nine isotopologues: ¹⁶O¹²C¹⁶O (626), ¹⁶O¹³C¹⁶O (636), ¹⁶O¹²C¹⁸O (628), ¹⁶O¹²C¹⁷O (627), ¹⁶O¹³C¹⁸O (638), ¹⁶O¹³C¹⁷O (637), ¹⁸O¹²C¹⁸O (828), ¹⁷O¹²C¹⁸O (728) and ¹⁸O¹³C¹⁸O (838). Calculated line positions, line intensities, Lorentz half-width and pressure-induced shift coefficients for self- and air-broadening are taken from our recent measurements and are presented for the Voigt molecular line shape. The database includes line intensities for 108 bands measured using the McMath-Pierce Fourier transform spectrometer located on Kitt Peak, Arizona. The available broadening parameters (half-widths and pressure-induced shifts) of ¹⁶O¹²C¹⁶O are applied to all isotopologues. Broadening coefficients are computed using empirical expressions that have been fitted to the experimental data. There are limited data for the temperature dependence of widths and so no improvement has been made for those parameters. The line intensities included in the catalog vary from 4×10⁻³⁰ to 1.29×10⁻²¹ cm⁻¹/(molecule cm⁻²) at 296 K. The total integrated intensity for this spectral interval is 5.9559×10⁻²⁰ cm⁻¹/(molecule cm⁻²) at 296 K.     

ABSORPTION INTENSITIES, PRESSURE-BROADENING AND LINE MIXING PARAMETERS OF SOME LINES OF NH3 IN THE ν4 BAND

The intensities and foreign gas broadening coefficients of 57 selected lines of the ν₄ band of NH₃ have been measured in the region of 1550 cm^-1 using a high resolution Brucker Fourier transform spectrometer. The line intensities were obtained by using the methods of absorbance at the line center and by fitting Voigt profiles to the measured shapes of the lines. The latter method also provides the collisional widths of the lines. In addition, collision cross relaxation coefficients of O₂ and air foreign gases were measured for 9 doublets of NH₃ in the ν₄ band. The J and K quantum numbers dependencies of pressure-broadening coefficients and line intensities are discussed. The observed air broadening and cross relaxation coefficients were found to be in reasonable quantitative agreement with the concentration-weighted average of the N₂ and O₂ broadening coefficients. The comparison of our present and previous results obtained for the NH₃–H₂, NH₃–air, NH₃–N₂ and NH₃–CO₂ collisions shows an increase of the pressure broadening and cross relaxation coefficients with quadrupole moment of the foreign gas. The analysis of the line intensities was based on the third-order theory of line strengths and yields effective transition moments, vibrational band strengths and correction parameters of the symmetric and antisymmetric partial bands of the fundamental ν₄ band.     

Measurements of O2-broadening and -shifting parameters of water vapor spectral lines in the second hexad region

Oxygen pressure induced broadening and shifting coefficients for water vapor absorption lines in the 8600–9010 cm⁻¹ region have been measured and calculated. The spectra were recorded with a Bruker IFS 125HR spectrometer at a spectral resolution of 0.01 cm⁻¹ for lines with angular moment of the upper states up to 10. Calculations of line broadening and shifting coefficients are performed using a semi-empirical approach. The method is based on the impact theory of broadening, and includes the correction factors whose parameters can be determined by fitting the broadening or shifting coefficients to the experimental data. The comparison of our calculations with the experimental values argues that the semi-empirical method is quite acceptable for the determination of the water vapor absorption line profile parameters.     

Self-, Nitrogen-, and Oxygen-Broadening Coefficient Measurements in the ν1 Band of H2O Using a Difference Frequency Generation Spectrometer at 3 μm

In this paper we investigate the mid-infrared spectrum of the H₂¹⁶O molecule between 3367 and 3447 cm⁻¹ to study the gas-collision-broadened linewidths. The coherent radiation used in this experiment is produced through difference frequency generation in a periodically poled lithium niobate crystal. The spectroscopic analysis has concerned nine H₂O lines in the ν₁ fundamental vibrational band. For these lines the self-, N₂-, and O₂-broadening coefficients are measured at room temperature. From these data, the widths due to air broadening are also determined. The experimental collisional broadening coefficients are compared with other experimental data and with theoretical calculations based on the Anderson-Tsao-Cornutte and Robert-Bonamy theories. Lineshape analysis is performed using both the standard Voigt profile and the Nelkin-Ghatak profile for the hard collision regime. For all the investigated lines the agreement between the Voigt profile and the measured profiles is found to be good.     

Tunable infrared diode laser measurements of line strengths and collision widths of 12C16O at room temperature

A tunable diode laser was used to scan 33 vibration-rotation lines in the fundamental band of CO in room-temperature CO-N₂ and CO-Ar mixtures. Each absorption record was fitted with a Voigt profile from which the line strength and collision width were determined. The fundamental band strength of ¹²C¹⁶O at 273.2°K was determined to be 283±4 cm^-2 atm^-1. Results are also presented for the rotational quantum number dependence of the collision width for broadening by N₂ and Ar.     

Line strengths and self-broadening coefficients of carbon dioxide isotopologues (CO2 and OCO) near 2.04 μm for the in situ laser sensing of the Martian atmosphere

A diode laser spectrometer was used in the laboratory to study ¹³CO₂ and ¹⁸O¹²C¹⁶O line intensities and self-broadening coefficients near 2.04 μm. The spectral region ranging from 4896 to 4903 cm⁻¹, which is suitable for in situ laser sensing of both isotopologues in the lower Martian atmosphere, was investigated using a distributed feedback GaInSb diode laser. Five lines of the (2 0⁰ 1)_II←(0 0 0) band of ¹³CO₂ and seven lines of the (2 0⁰ 1)_II←(0 0 0) band of ¹⁸O¹²C¹⁶O were carefully revisited. The measured intensities and self-broadening coefficients were thoroughly compared with relevant molecular databases.     

N2 and O2 pressure broadening and pressure shift in the 4ν2 band of OCS

To measure accurately OCS concentrations in planetary atmospheres, it is important to know precisely nitrogen and oxygen pressure broadening and pressure-induced shift coefficients for the lines used in the retrievals. We present in this study the corresponding coefficients for lines of the P and R branches of the 4ν₂ band of the primary isotopologue of carbonyl sulfide (¹⁶O¹²C³²S).For this purpose, infrared absorption spectra of a natural carbonyl sulfide (OCS) gas sample were recorded at an unapodized resolution of 0.004 cm⁻¹, at room temperature for different pressures of N₂ and O₂, using a Bruker IFS125HR spectrometer at the LISA Laboratory in France. The line parameters were derived using the multispectrum fitting method applied to the measured shapes of the lines, including the interference effects caused by the line overlaps.The results are compared with earlier measurements and with values calculated using a semi-classical model based upon the Robert and Bonamy formalism that reproduces rather well the experimental m (m=−J for P(J) lines and m=J+1 for R(J) lines) quantum number dependence of the N₂ and O₂ broadening coefficients. On the other hand most of the lines studied here have positive shift coefficients, which do not show any systematic dependence on m. However, in previous studies of the ν₃, 2ν₃ and ν₂ bands, these coefficients were negative for all lines.     

The continuum absorption in H2O+N2 mixtures in the 2000-3250 cm spectral region at temperatures from 326 to 363 K

The absorption spectra of H₂O+N₂ mixtures, as well, as the spectra of pure gases, have been measured using a Fourier-transform infrared spectrometer at a resolution of 0.1 cm⁻¹. The sample temperatures were 326, 339, 352, and 363 K. Water vapor pressures varied from 8 (60 torr) to 34.5 kPa (259 torr). The nitrogen pressure was kept constant at about 414 kPa (4.1 atm). The path length was 100 m. The continuum absorption coefficients obtained in the spectral range 2000-3250 cm⁻¹ (3.1-5 μm) do not depend significantly on temperature, as is predicted by the well known MT_CKD model. But there are significant deviations in the continuum spectral behavior and magnitude. Around 2050 cm⁻¹ the measured absorption coefficients C_f are about two times larger than those of the model. This deviation grows rapidly at shorter wave lengths, reaching a maximum of two orders of magnitude in the middle of the window at 2500 cm⁻¹. At this point, the deviation starts to decrease significantly and around 3100 cm⁻¹ our results are in agreement with the MT_CKD model. This behavior of the deviation is due to the broad and structureless feature in the region of the nitrogen fundamental band. Most likely, this feature is the N₂ fundamental band component, induced by collisions between H₂O and N₂ molecules. The data obtained and a comparison with the results from the other available sources are presented.     

Low and room temperature measurements and calculations of O2-broadening coefficients in the ν3 band of CS2

O₂-broadening coefficients have been measured for 16 lines in the P and R branches of the fundamental ν₃ band of ¹²C³²S₂ at room and low temperatures (298.0, 273.2, 248.2, 223.2, and 198.2 K), using a tunable diode laser spectrometer and a low temperature cell. These lines from P(62) and R(64) are located in the spectral range 1519-1547 cm⁻¹. The collisional half-widths are obtained by fitting each observed profile with the Voigt and Rautian lineshape models. The broadening coefficients have also been calculated at all experimental temperatures using a semiclassical calculation performed by considering in addition to the electrostatic quadrupole-quadrupole interaction, a simple anisotropic contribution. Finally, from all the results, the parameter n of the temperature dependence of the broadening coefficients has been determined both experimentally and theoretically.     

Air-broadening coefficients of the HO2 radical in the 2ν1 band measured using cw-CRDS

In this paper we present measurements of the air-broadening coefficients of HO₂ at room temperature in the 2ν₁ band around 1.5 microns. The HO₂ radicals were created by flash photolysis of SOCl₂ in a flow of O₂/CH₃OH mixtures. To observe air-broadening, N₂ (79%) and O₂ (21%) were added using calibrated flow controllers and a total pressure controller. The total pressure was monitored in parallel using a capacitive pressure gauge. Air-broadening coefficients at 296 K were determined for 34 absorption lines between 6631 and 6671 cm⁻¹. The air-broadening coefficients of HO₂ show a rotational dependence (decreasing from about 0.14 cm⁻¹/atm for N″ = 3 to about 0.09 cm⁻¹/atm for N″ = 10). No evidence for collisional narrowing was observed.     

Ar- and air-broadening coefficients in the ν3 band of CS2 at room and low temperatures

Using a diode-laser spectrometer, Ar-broadening coefficients for 16 spectral lines in the fundamental ν₃ band of CS₂ have been measured at five temperatures: 298.0, 273.2, 248.2, 223.2 and 198.2 K. These lines with J values ranging from 2 to 64 are located in the spectral range 1519-1547 cm⁻¹. The broadening coefficients are also calculated from a semiclassical impact model performed by using a simple empirical intermolecular potential. From the theoretical and experimental results obtained at the different temperatures, we have determined the n exponent values governing the temperature dependence of the broadening coefficients. The air-broadening coefficients for four spectral lines in the ν₃ band of CS₂ have also been measured experimentally at the same temperatures. They are compared to the values derived from those obtained previously for the perturbers N₂, O₂ and also Ar.     

Half-width temperature dependence of nitrogen broadened lines in the ν2 band of H2O

Forty-seven N₂ broadened water vapor line-widths have been measured in the 1845-2140 cm⁻¹ spectral range with a Fourier Transform spectrometer in the 258-330 K temperature range at a spectral resolution of 0.005 cm⁻¹ for the lines with upper state rotational quantum number up to 16. The measured exponents of the temperature dependence of the width exhibit a large range of values from 1.60 to −0.86. Theoretical calculations were made using a semi-empirical technique based on the Anderson theory. The calculated broadening coefficients as well as the temperature exponents for the half-width agree satisfactory with measured values.     

Stark spectroscopy with the CO laser: The ν3 fundamental band of H2CO

The ν₃ fundamental band of H₂CO (CH₂ scissoring motion) has been studied by means of CO laser Stark spectroscopy and conventional infrared absorption spectroscopy. The primary aim of the work was to determine the dipole moment of H₂CO in the v₃ = 1 state, and the value determined was 2.3250 ± 0.0025 D. The spectrum was analyzed with the inclusion of the Coriolis interactions among ν₃, ν₄, and ν₆ so that “true” rotational constants were determined for ν₃; “effective” constants obtained by ignoring these interactions were also determined. The ν₃ band origin was determined to be 1500.174 ± 0.002 cm^?1. The H₂CO spectrum was also used as a means of determining the frequencies of some ¹³C¹⁶O and ¹²C¹⁸O laser lines in the 1500 cm^?1 region relative to ¹²C¹⁶O lines.     

Measurements and theoretical calculations of N2-broadening and N2-shift coefficients in the ν2 band of CH3D

In this paper, we report measured Lorentz N₂-broadening and N₂-induced pressure-shift coefficients of CH₃D in the ν₂ fundamental band using a multispectrum fitting technique. These measurements were made by analyzing 11 laboratory absorption spectra recorded at 0.0056 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 10.2 and 25 cm. The total sample pressures ranged from 0.98 to 402.25 Torr with CH₃D volume mixing ratios of 0.01 in nitrogen. We have been able to determine the N₂ pressure-broadening coefficients of 368 ν₂ transitions with quantum numbers as high as J″ = 20 and K = 16, where K″ = K′ ≡ K (for a parallel band). The measured N₂-broadening coefficients range from 0.0248 to 0.0742 cm⁻¹ atm⁻¹ at 296 K. All the measured pressure-shifts are negative. The reported N₂-induced pressure-shift coefficients vary from about −0.0003 to −0.0094 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 4.7%. The N₂-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 in good overall agreement with the experimental data (8.7%). The N₂-pressure shifts whose vibrational contribution is derived from parameters fitted in the ^QQ-branch of self-induced shifts of CH₃D, are also in reasonable agreement with the scattered experimental data (20% in most cases).