Measurements of high-pressure CO2 absorption near 2.0 μm and implications on tunable diode laser sensor design

A tunable diode laser (TDL) is used to measure the absorption spectra of the R46 through R54 transitions of the 20012←00001 band of CO₂ near 2.0 μm (5000 cm⁻¹) at room temperature and pressures to 10 atm (densities to 9.2 amagat). Spectra are recorded using direct absorption spectroscopy and wavelength modulation spectroscopy with second-harmonic detection (WMS-2f) in a mixture containing 11% CO₂ in air. The direct absorption spectra are influenced by non-Lorentzian effects including finite-duration collisions which perturb far-wing absorption, and an empirical χ-function correction to the Voigt line shape is shown to greatly reduce error in the spectral model. WMS-2f spectra are shown to be at least a factor of four less-influenced by non-Lorentzian effects in this region, making this approach more resistant to errors in the far-wing line shape model and allowing a comparison between the spectral parameters of HITRAN and a new database which includes pressure-induced shift coefficients. The implications of these measurements on practical, high-pressure CO₂ sensor design are discussed.     

Calculation of solar radiation atmospheric absorption with different H2O spectral line data banks

A comparison of the atmospheric absorption calculated with different data banks of water vapour absorption lines is made. The HITRAN database, Barber-Tennyson line list (BT2), calculation of Partridge and Schwenke (PS) are considered. The contribution of H₂O lines, absent in HITRAN, to the atmospheric transmission, calculated with 10 cm⁻¹ spectral resolution in the 10 000-20 000 cm⁻¹ spectral region is up to 1.5% for a vertical path and 4% for a solar zenith angle of 70 deg. The highest difference is observed in the 940 nm band. The incoming fluxes of solar radiation, measured by a rotating solar spectroradiometer, were modeled with BT2 and HITRAN database. The difference between measured and calculated fluxes does not exceed the instrumental uncertainties.     

Experimental study of H2O spectroscopic parameters in the near-IR (6940-7440 cm) for gas sensing applications at elevated temperature

Tunable diode laser (TDL) absorption sensors of water vapor are attractive for temperature, gas composition, velocity, pressure, and mass flux measurements in a variety of practical applications including hydrocarbon-fueled combustion systems. Optimized design of these sensors requires a complete catalog of the assigned transitions with accurate spectroscopic data; our particular interest has been in the 2ν₁, 2ν₃, and ν₁+ν₃ bands in the near-IR where telecommunications diode lasers are available. In support of this need, fully resolved absorption spectra of H₂O vapor in the spectral range of 6940-7440 cm⁻¹ (1344-1441 nm) have been measured as a function of temperature (296-1000 K) and pressure (1-800 Torr), and quantitative spectroscopic parameters inferred from these spectra compared to published data from Toth, HITRAN 2000 and HITRAN 2004. The peak absorbances were measured for more than 100 strong transitions at 296 and 828 K, and linestrengths determined for 47 strong lines in this region. In addition to reference linestrengths S(296 K), the air-broadening coefficients γ_air(296 K) and temperature exponents n were inferred for strong transitions in five narrow regions, near 7185.60, 7203.89, 7405.11, 7426.14 and 7435.62 cm⁻¹ that had been targeted as attractive for future diagnostics applications. Most of the measured results, determined within an accuracy of 5%, are found to be in better agreement with HITRAN 2004 than with earlier editions of this database. Large discrepancies (>10%) between measurements and HITRAN 2004 database are identified for some of the probed transitions. These new spectroscopic data for H₂O provide a useful test of the sensor design capabilities of HITRAN 2004 for combustion and other applications at elevated temperatures.     

Tunable diode laser absorption measurement of oxygen A-band line strengths

Line strength measurements and pressure-broadening coefficients for the oxygen A-band (b¹Σ_g ⁺ X³Σ_g ^-) at 13122 cm^-1 using tunable diode laser absorption spectroscopy are reported. Diode lasers are scanned over individual lines and the absorption at different pressures is recorded; from these data the line strength for each transition is obtained. Average values for each transition are compared to those previously published, and in particular a comparison with the HITRAN database is presented. Line strengths reported here are 5–10% lower than the HITRAN values. PACS 33.20.-t; 33.70.Fd     

Measurements and modelling of high pressure pure CO2 spectra from 750 to 8500 cm. I—central and wing regions of the allowed vibrational bands

Precise modelling of infrared absorption by carbon dioxide is of primary importance for radiative transfer calculations in CO₂-rich atmospheres like those of Venus and Mars. Despite various measurements and theoretical models dedicated to this subject, accurate data at different temperatures and pressures are still lacking in numerous spectral regions. In this work, using two Fourier Transform Spectrometers, we have measured spectra of pure CO₂ in a large spectral region range, from 750 to 8500 cm⁻¹ at various densities (3-57 amagat) and temperatures (230-473 K). Comparisons between measured dipolar absorption bands and spectra calculated with the widely used Lorentz line shape show very large discrepancies. This result is expected since the Lorentz approach neglects line-coupling effects due to intermolecular collisions which transfer absorption from the wings to the band center. In order to account for this effect, a theoretical approach based on the impact and Energy Corrected Sudden approximations has been developed. Comparisons of this model with numerous laboratory spectra in a wide range of pressure, temperature and spectral domain show satisfactory agreements for band centers and near wing regions where the impact approximation is valid. However, as expected, due to the breakdown of the impact approximation, the model fails when considering far wing regions. In the absence of precise models accounting for line-mixing and finite collision duration (non impact) effects, empirical approximations are proposed in order to model the far wings.     

Comparison of band model and integrated line-by-line synthetic spectra for methane in the 2.3 μm region

The 2.3 μm spectral region of methane can be used to retrieve cloud properties of planetary spectra, provided parameters for the methane spectrum are known. Two standard techniques for calculating absorption spectra in this region are compared here. A Voigt profile Mayer-Goody random band model is applied, using coefficients empirically fitted by Fink et al. to CH₄ spectra recorded with high absorping amounts at 10 cm^?1 resolution. Calculation of the absorption is also done with a line-by-line direct integration method for the same gas conditions using molecular parameters obtained by combining an older unpublished list of observed positions and estimated line strengths (derived from 0.04 cm^?1 resolution data) with quantum assignments from the literature. The molecular parameters have been evaluated for the 4180–4590 cm^?1 region by comparing new laboratory spectra with 0.01 cm^?1 resolution recorded at 296 and 153K with synthetic spectra calculated at the same conditions. The deficiencies of the molecular parameters and random band coefficients for this spectral region of CH₄ are then discussed qualitatively and demonstrated by comparing 10 cm^?1 resolution synthetic spectra calculated by both methods for the same gas conditions at 296, 153, and 55 K.Curves of growth of the total equivalent width are calculated at 296 and 55K for a pathlength of 50 cm and pressures up to 10 atm. Changing the mean line spacing in the band model gives better agreement between the spectra calculated by the two techniques at low gas temperatures. The required multiplier has been determined for the mean line spacing for pressures from 10^?6 to 10^?1 atm at 55, 100, and 150 K.     

Effect of changes of the HITRAN database on transmittance calculations in the near-infrared region

In order to retrieve from high spectral resolution measurements with high accuracy, it is necessary to be able to evaluate the transmittance precisely. However, the uncertainty of the spectroscopic parameters is one of the most important contributions that affect the accuracy of transmittance. HITRAN is a compilation of spectroscopic parameters which has been updated several times. The transmittance calculations using the line parameters from the HITRAN’2000 database and the HITRAN’2004 database have been compared over the near infrared range from 4200 to 10,000 cm^?1. The differences between calculated transmittances over this spectral range are mainly caused by changes of the line parameters for H₂O, CO₂ and CH₄. For the tropical atmosphere, the differences are very prominent. Transmittance calculations for the sub-arctic winter atmosphere are less sensitive to the changes in the HITRAN database than those for the tropical atmosphere; but, the changes of line parameters still can not be ignored when considering the relative differences. For example, the relative difference is ～35% at 5073.3 cm^?1 with 0.2 cm^?1 spectral resolution. The comparisons have shown that it is important to pay attention to the changes of line parameters of the HITRAN database or to use the latest edition so as to improve the accuracy of atmospheric sounding with high spectral resolution.     

Air pressure broadening and shifting of high-J lines of (00011) ← (00001) band of CO2

The absorption spectra of carbon dioxide (isotope 626, natural abundance in air, ambient temperature) have been studied at total pressures 68-570 Torr with spectral resolution 0.003-0.005 cm⁻¹. The spectra were measured in the spectral domain of 2273-2393 cm⁻¹ by FTIR spectrometer Bruker IFS 125 HR equipped with White-type multipass cell (6.4-41.6 m) and with a cell having 10 cm optical path length. Pressure broadening and shift coefficients were obtained from a series of spectra by means of a nonlinear least-squares spectral fitting technique for the lines of the (00011)←(00001) band with rotational quantum number up to J=82. For fitting of the individual line shapes, we used the Voigt profile with pre-calculated Doppler broadening parameter. The experimental pressure broadening and shift coefficients are compared with the values available in spectroscopic databases HITRAN 2008 and Carbon Dioxide Spectroscopic Databank (CDSD-296) and with other experimental values reported in the literature.     

Intensity measurements of H2O lines in the spectral region 8000-9350 cm

This paper presents new measurements of H₂¹⁶O lines performed on spectra recorded with the GSMA Fourier Transform Spectrometer (FTS). Our experimental conditions allow one to obtain new line intensity measurements from 10⁻²⁵ to 10⁻²¹ cm/molec at 296 K and self-broadening coefficients in the spectral range centered at 8800 cm⁻¹. In the HITRAN database, data reported for this region is taken from the work of Mandin et al. (1988) [8] and [9] and several articles pointed out problems on the line intensities. We present in this paper some intensity comparisons, first with the HITRAN database, and then with the recent article of Tolchenov and Tennyson (2005) [3]. We finish by a comparison on self-broadening coefficients.     

NO fundamental and first hot ro-vibrational line frequencies from MIPAS/Envisat atmospheric spectra

MIPAS (Michelson Interferometer for Passive Atmosphere Sounding) is a high spectral resolution interferometer (0.035 cm⁻¹ unapodized) covering a very wide spectral range (from 4.16 to 16.4 μm) with high sensitivity that was successfully launched on the 1st of March 2002 on the European Envisat satellite. MIPAS has measured spectra of the Earth’s upper atmosphere in the 4.3 μm region with the highest spectral resolution so far reached in this altitude region. This high spectral resolution permitted to obtain the frequency position of ro-vibrational NO⁺ transitions with an unprecedented accuracy. It has been found that the spectral line positions of the NO⁺ (1-0) ro-vibrational band are shifted by about ∼0.15 cm⁻¹ with respect to those listed in the HITRAN 2004 compilation. Also, spectral line positions of the NO⁺ (2-1) ro-vibrational band are shifted by approximately 0.05-0.1 cm⁻¹ with respect to those listed in the HITRAN 2004 compilation. A new set of Hamiltonian constants for NO⁺ has been derived from MIPAS data which is suggested to be used in future HITRAN compilations.     

Measurement of the continuum absorption coefficient of water vapor near 14400 cm−1 (0.694 μm)

The continuum absorption coefficient (CAC) of water vapor (k _cont) in the visible region is determined for the first time from the data of laboratory measurements. For this purpose, the absorption spectra of water vapor in the region 14395–14402 cm^?1 are recorded with the aid of a high-sensitivity photoacoustic spectrometer with a frequency-tunable single-pulse ruby laser, and the absorption measured in this transparency microwindow is compared with that calculated based on the HITRAN 2004 data bank. In the spectral region under study, k _cont = (0.53 ± 0.18) × 10^?9 cm^?1 mbar^?1 at a total pressure of a water vapor-nitrogen mixture of 1000 mbar and a temperature of 295 K. This value of the CAC is roughly 23% higher than the CAC value in the IO-CKD model of the continuum.     

Line parameters for the 01111-00001 band of COO from SOIR measurements of the Venus atmosphere

CO₂ is the major constituent of the atmosphere of Venus. Absorption lines due to its ¹²C¹⁶O¹⁸O isotopologue have been observed for the first time in Venus spectra in the 2930-3015 cm⁻¹ spectral region, where the HITRAN database does not contain any line from this isotopologue. The measurements were performed by the SOIR instrument, which is part of the SPICAV/SOIR instrument on board the Venus Express mission of ESA. SOIR measured the atmospheric transmission of the upper atmosphere of Venus (z>70 km) by performing a solar occultation experiment using the atmosphere as a gigantic absorption cell. The identification of this newly observed band was first made recently from Mars atmosphere observations by US colleagues. We have made independent theoretical calculations of the positions of the lines of this new 01111-00001 absorption band, which coincide perfectly with the positions of the observed lines. Assuming an oxygen isotopic ratio similar to the one measured previously in the lower atmosphere of Venus, the line strengths of each observed line are deduced and listed.     

Calculations and measurements of N2O absorption at high temperature in the 4.5 μm region

An approximate N₂O spectroscopic database suitable for high temperature and medium resolution applications has been created in the 4.5 μm region. Intensities of ¹⁴N₂ ¹⁶O hot bands have been extrapolated pragmatically from the v₃ band intensity and energies of vibrational levels have been computed by diagonalization of the effective Hamiltonian. The new parameters have been merged with the data available in the HITRAN database and in the recent experimental work of Toth. The entire list has then been used to generate individual line parameters. Pure N₂O spectra have been recorded with a Fourier Transform spectrometer up to 900 K and with 1 cm⁻¹ resolution. A good agreement between these spectra and line-by-line calculations using the new database is obtained while the use of HITRAN greatly underestimates absorption at high temperature.     

Infrared absorption cross sections for methanol

Infrared absorption cross sections for methanol, CH₃OH, have been determined near 3.4 and 10 μm from spectra recorded using a high-resolution FTIR spectrometer (Bruker IFS 125HR) and a multipass cell with a maximum optical path length of 19.3 m. Methanol/dry synthetic air mixtures were prepared and spectra were recorded at 0.015 cm^?1 resolution (calculated as 0.9/MOPD) at a number of temperatures and pressures (50–760 Torr and 204–296 K) appropriate for atmospheric conditions. Intensities were calibrated using composite methanol spectra taken from the Pacific Northwest National Laboratory (PNNL) IR database. The new measurements in the 10 μm region indicate problems with the existing methanol spectroscopic line parameters in the HITRAN database, which will impact the accuracy of satellite retrievals.     

FTIR measurements of CO2 line positions and intensities at high temperature in the 3700-3750 cm spectral region

Positions and intensities for 453 spectral lines in 12 rovibrational bands of ¹²C¹⁶O₂ have been determined between 3700 and 3750 cm⁻¹. At three temperatures (294, 500, and 698 K) eight spectra have been recorded at a pressure around 5 mbar and for an absorption path of about 190 cm⁻¹ using a Bomen DA3 Fourier transform spectrometer (4 × 10⁻³ cm⁻¹ resolution). Some of the measured positions and intensities can be compared with recent experimental results that validate the experimental set-up and the data analysis procedure. The results are also compared with the values listed in the HITRAN 2000 database. If the agreement is generally good, discrepancies are observed for three hot bands.     

Updated database plus software for line-mixing in CO2 infrared spectra and their test using laboratory spectra in the 1.5-2.3 μm region

In a previous series of papers, a model for the calculation of CO₂-air absorption coefficients taking line-mixing into account and the corresponding database/software package were described and widely tested. In this study, we present an update of this package, based on the 2008 version of HITRAN, the latest currently available. The spectroscopic data for the seven most-abundant isotopologues are taken from HITRAN. When the HITRAN data are not complete up to J″=70, the data files are augmented with spectroscopic parameters from the CDSD-296 database and the high-temperature CDSD-1000 if necessary. Previously missing spectroscopic parameters, the air-induced pressure shifts and CO₂ line broadening coefficients with H₂O, have been added. The quality of this new database is demonstrated by comparisons of calculated absorptions and measurements using CO₂ high-pressure laboratory spectra in the 1.5-2.3 μm region. The influence of the imperfections and inaccuracies of the spectroscopic parameters from the 2000 version of HITRAN is clearly shown as a big improvement of the residuals is observed by using the new database. The very good agreements between calculated and measured absorption coefficients confirm the necessity of the update presented here and further demonstrate the importance of line-mixing effects, especially for the high pressures investigated here. The application of the updated database/software package to atmospheric spectra should result in an increased accuracy in the retrieval of CO₂ atmospheric amounts. This opens improved perspectives for the space-borne detection of carbon dioxide sources and sinks.     

High-resolution photoacoustic and direct absorption spectroscopy of main greenhouse gases by use of a pulsed entangled cavity doubly resonant OPO

An entangled cavity doubly resonant optical parametric oscillator (ECOPO) has been developed to provide tunable narrow line width (<100 MHz) pulsed (8 ns) radiation over the 3.8–4.3 μm spectral range at a multi-kilohertz repetition rate with up to 100-W peak power. We demonstrate that coarse single mode tuning is obtained over the full spectral range of oscillation (300 cm⁻¹), while automated mode-hop-free fine tuning is carried out over more than 100 GHz. High-resolution spectra of main greenhouse gases (CO₂, N₂O, SO₂ and CH₄) have been obtained in good agreement with calculated spectra from the HITRAN database. These experiments outline the unique capabilities of the ECOPO for multi-gas sensing based on direct absorption as well as photoacoustic spectroscopy.     

Infrared absorption cross sections for ethane (C2H6) in the 3 μm region

Infrared absorption cross sections for ethane have been measured in the 3 μm spectral region from spectra recorded using a high-resolution FTIR spectrometer (Bruker IFS 125/HR). Results are presented for pure ethane gas from spectra recorded at 0.004 cm⁻¹ resolution and for mixtures with dry synthetic air from spectra obtained at 0.015 cm⁻¹ resolution (calculated as 0.9/MOPD using the Bruker definition of resolution), at a number of temperatures and pressures appropriate for atmospheric conditions. Intensities were calibrated using three ethane spectra (recorded at 278, 293, and 323 K) taken from the Pacific Northwest National Laboratory (PNNL) IR database.     

Mid-infrared absorption cross sections for acetone (propanone)

Infrared absorption cross sections for acetone (propanone) have been determined in the 830-1950 cm⁻¹ spectral region from spectra recorded using a high-resolution FTIR spectrometer (Bruker IFS 125HR) and a multipass cell with a maximum optical path length of 19.3 m. The spectra of mixtures of acetone with dry synthetic air were recorded at 0.015 cm⁻¹ resolution (calculated as 0.9/MOPD using the Bruker definition of resolution) at a number of temperatures between 194 and 251 K and pressures appropriate for atmospheric conditions. Intensities were calibrated using three acetone spectra (recorded at 278, 293 and 323 K) taken from the Pacific Northwest National Laboratory (PNNL) IR database. The new absorption cross sections have been combined with previous high spectral resolution results to create a more complete set of acetone absorption cross sections appropriate for atmospheric remote sensing. These cross sections will provide an accurate basis for upper tropospheric/lower stratospheric retrievals of acetone in the mid-infrared spectral region from ACE and MIPAS satellite data.     

Laser-Raman spectra of argon-iodine interactions

Resonance Raman spectra of iodine-argon interactions at relatively high argon pressures (1–40 atm) are presented. It is shown that the decrease in the vibrational frequency from 213 cm^-1 for iodine molecule to 197 cm^-1 for Ar-I₂ is consistent with the formation of an argon-iodine complex catalyzed by the glass surface, or possibly with a weak Ar-I vibration.