Temperature dependence of the absorption spectrum of CH4 by high resolution spectroscopy at 81 K: (I) The region of the 2ν3 band at 1.66 μm

In a recent contribution, (Gao B, Kassi S, Campargue A. Empirical low energy values for methane transitions in the 5852-6181 cm⁻¹ region by absorption spectroscopy at 81 K. J Mol Spectrosc 2009;253:55-63.), the low energy values of methane transitions between 1.71 and 1.62 μm were derived from the variation of the line intensities between 296 and 81 K. The line intensities at 81 K were retrieved from the high resolution absorption spectrum of methane recorded at liquid nitrogen temperature by direct absorption spectroscopy using a cryogenic cell and a series of distributed feed back (DFB) diode lasers. For the line intensities at 296 K, the values provided by the HITRAN database were used. As a consequence of the relatively high intensity cut off (4×10⁻²⁴ cm/molecule) of the HITRAN line list in the considered region, the lower energy values were derived for only 845 of the 2187 transitions measured at 81 K. In the present work, our line list was extended by the retrieval of many weak line intensities leading to a set of 3251 transitions. The minimum value of the measured line intensities (at 81 K) is on the order of 10⁻²⁶ cm/molecule. In relation with the project “Greenhouse Gases Observing Satellite” (GOSAT), a much more complete line list for CH₄ at 296 K has become available (intensity cut off of 4×10⁻²⁶ cm/molecule). By applying the two temperature method to our line intensities at 81 K and GOSAT intensities at 296 K, the lower energy values of 2297 transitions could be derived. These transitions represent 99.1% and 90.8% of the total absorbance in the region, at 81 and 296 K respectively. This line list provided as Supplementary Material allows then accounting for the temperature dependence of CH₄ absorption below 300 K. The investigated spectral range is dominated by the 2ν₃ band near 6005 cm⁻¹ which is of particular interest for atmospheric retrievals. The factor 2 narrowing of the Doppler linewidth from room temperature down to 81 K has allowed the resolution of a number of 2ν₃ multiplets and improving the line intensity retrievals. A detailed comparison with GOSAT and HITRAN line lists has revealed a number of possible improvements.     

Experimental low energy values of CH4 transitions near 1.33 μm by absorption spectroscopy at 81 K

The high resolution absorption spectrum of methane has been recorded at liquid nitrogen temperature by direct absorption spectroscopy between 1.36 and 1.30 μm (7351-7655 cm⁻¹) using a cryogenic cell and a series of distributed feed back (DFB) diode lasers. The investigated spectral range corresponds to the high energy part of the icosad dominated by the ν₂+2ν₃ band near 7510 cm⁻¹. The positions and strengths at 81 K of 3473 transitions were obtained from the spectrum analysis. The minimum value of the measured line intensities (at 81 K) is on the order of 10⁻²⁶ cm/molecule, i.e. significantly lower than the intensity cut off of the HITRAN database in the region (4×10⁻²⁵ cm/molecule at 296 K). From the variation of the line strength between 81 and 296 K, the low energy values of 1273 transitions could be determined. They represent 69% and 81% of the absorbance in the region at 296 and 81 K, respectively. The obtained results are discussed in relation with the few rovibrational assignments previously reported in the region.     

High sensitivity absorption spectroscopy of methane at 80 K in the 1.58 μm transparency window: Temperature dependence and importance of the CH3D contribution

The high resolution absorption spectrum of methane in the 1.58 μm transparency window has been recorded at room temperature and at 79 K by CW-Cavity Ring Down Spectroscopy using a cryogenic cell and a series of Distributed Feed Back (DFB) diode lasers. The achieved sensitivity (α_min ∼ 3 × 10⁻¹⁰ cm⁻¹) has allowed for a detailed characterization of the 6289-6526 cm⁻¹ region which corresponds to the lowest opacity of the transparency window. A list of 6868 and 4555 transitions with intensities as weak as 1 × 10⁻²⁹ cm/molecule was constructed from the recordings at 297 and 79 K, respectively. By comparison with a spectrum of CH₃D recorded separately by Fourier Transform Spectroscopy, 1282 and 640 transitions of monodeuterated methane, CH₃D, in natural abundance in our sample were identified at 297 and 79 K, respectively.The rotational temperature determined from the intensity distribution of the 3ν₂ band of CH₃D (79.3 K) was found in good agreement with the temperature value previously obtained from the Doppler line broadening. The reduction of the rotational congestion by cooling down to 79 K reveals a spectral region near 6300 cm⁻¹ where CH₃D transitions are dominant.The low energy values of the transitions observed both at 79 K and at room temperature were derived from the variation of their line intensities. These transitions with lower energy determination represent 93.9% and 68.4% of the total absorbance in the region, at 79 K and room temperature, respectively. The quality of the obtained empirical low energy values is demonstrated for CH₄ by the marked propensity of the empirical low J values to be close to integers. The line lists at 79 K and room temperature provided as Supplementary Material allow accounting for the temperature dependence of methane absorption between these two temperatures. The investigated region covering the 5ν₄ band of the ¹²CH₄ isotopologue will be valuable for the theoretical treatment of this band which is the lowest energy band of the icosad.     

HCOOH high-resolution spectroscopy in the 9.18 μm region

We report on highly accurate absolute frequency measurement against a femtosecond frequency comb of six saturated absorption lines of formic acid (HCOOH) with an accuracy of 1 kHz. We also report the frequency measurement of 17 other lines with an accuracy of 2 kHz. Those lines are in quasi coincidence with the 9R(36) to 9R(42) CO₂ laser emission lines and are probed either by a CO₂ or a widely tunable quantum cascade laser phase locked to a master CO₂ laser. The stability of HCOOH stabilized lasers is characterized by a fractional Allan deviation of 3.1 × 10⁻¹² τ^−1/2. They give suitable frequency references for Doppler-free two-photon spectroscopy.     

Acetonitrile (CH3CN) infrared absorption cross sections in the 3 μm region

High resolution infrared absorption cross sections of acetonitrile have been determined from spectra recorded in the 3 μm spectral region using a Bruker IFS 125 HR Fourier transform spectrometer (FTS) and a multipass White cell. The eleven synthetic air-broadened acetonitrile spectra were recorded at a resolution of 0.015 cm⁻¹ (calculated as 0.9/MOPD (Maximum Optical Path Difference), the Bruker definition of resolution) over a range of different temperatures and pressures that are representative of conditions in the Earth's atmosphere (50-760 Torr and 207-296 K). Intensities were calibrated using infrared spectra recorded at the Pacific Northwest National Laboratory (PNNL). These new cross sections will enable satellite retrievals of acetonitrile in the 3 μm region from atmospheric spectra recorded by satellite instruments, such as the ACE (Atmospheric Chemistry Experiment)-FTS.     

Infrared absorption cross-sections for acetaldehyde (CH3CHO) in the 3 μm region

A series of infrared absorption cross-sections for acetaldehyde has been measured in the 3 μm region from spectra obtained using a high-resolution Fourier transform spectrometer (Bruker IFS 125/HR). Results presented are for mixtures of acetaldehyde vapor combined with pure synthetic air taken at various temperatures and pressure to simulate atmospheric conditions found principally in the Earth's troposphere and lower stratosphere. Spectra were recorded at a resolution of 0.005 cm⁻¹ and intensities were calibrated using three acetaldehyde spectra (measured at 278, 298 and 323 K) provided by the Pacific Northwest National Laboratory (PNNL) IR database.     

Determination of the low energy values of CH4 transitions in the 2ν3 region near 1.66 μm from absorption spectra at 296 and 81 K

The high resolution absorption spectra of ¹³CH₄ were recorded at 81 K by differential absorption spectroscopy using a cryogenic cell and a series of distributed feed back (DFB) diode lasers and at room temperature by Fourier transform spectroscopy. The investigated spectral region corresponds to the high energy part of the ¹³CH₄ tetradecad dominated by the 2ν₃ overtone near 5988 cm⁻¹. Empirical line lists were constructed containing, respectively, 1629 ¹³CH₄ transitions detected at 81 K (5852-6124 cm⁻¹) and 3481 features (including 85 lines of ¹²CH₄) measured at room temperature (5850-6150 cm⁻¹); the smallest measured intensities are about 3 × 10⁻²⁶ and 4 × 10⁻²⁵ cm/molecule at 81 and 296 K, respectively. The lower state energy values were derived for 1196 ¹³CH₄ transitions from the variation of the line intensities between 81 and 296 K. These transitions represent 99.2% and 84.6% of the total absorbance in the region, at 81 and 296 K, respectively. Over 400 additional weak features were measured at 81 K and could not be matched to lines observed at room temperature. The quality of the resulting empirical low energy values is demonstrated by the excellent agreement with the already-assigned transitions and the clear propensity of the empirical low J values to be close to integers. The two line lists at 81 and at 296 K provided as Supplementary material will enable future theoretical analyses of the upper ¹³CH₄ tetradecad.     

Infrared absorption cross sections for acetone (propanone) in the 3 μm region

Infrared absorption cross sections for acetone (propanone), CH₃C(O)CH₃, have been determined in the 3 μm spectral region from spectra recorded using a high-resolution FTIR spectrometer (Bruker IFS 125 HR) 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 and pressures (50-760 Torr and 195-296 K) 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 water-vapor continuum and selective absorption in the 3-5 μm spectral region at temperatures from 311 to 363 K

The pure water-vapor continuum absorption in the 2.88 to 5.18 μm spectral region has been measured using a Fourier-transform infrared spectrometer at a resolution of 0.1 cm⁻¹. The sample temperatures and pressures varied from 311 to 363 K and from 2.8 kPa (21 Torr) to 34.5 kPa (259 Torr), respectively. The path lengths used in the study ranged from 68 to 116 m. Under these conditions, the continuum absorption in the middle of the 4 μm window is quite detectable reaching as high as 4%. The spectral processing included calculations to fit and remove the H₂O ro-vibrational structure. In the region around 5 μm, the absorption coefficients obtained are in good agreement with those of the commonly used MT_CKD continuum model. However at shorter wavelengths, the observed values significantly deviate from the model. Inspection of the present data as well as that of previous measurements leads to the conclusion that the MT_CKD model despite the latest updates significantly underestimates the rate of the continuum temperature dependence over the 4 μm atmospheric window. Line strengths for 189 H₂O transitions were obtained from the spectral processing. The deviation of these measured intensities from those listed in the HITRAN database is randomly scattered around zero to within several percents and no systematic trends were detected.     

Pressure broadening coefficients of ν5 fundamental band lines of CH3I at 7 μm measured by diode laser absorption spectroscopy

We have measured the room temperature pressure broadening coefficients, γ, of over 100 lines in five Q-branches of the ν₅ perpendicular band of methyl iodide (¹²CH₃I) using tuneable diode laser absorption spectroscopy. The profiles of individual lines in the ^PQ₂, ^PQ₄, ^PQ₅, ^PQ₆ and ^RQ₃ branches were recorded in a 1 m long White cell and at nitrogen or oxygen pressures up to 15 Torr. The lines were fitted to the Voigt profile to obtain the collision broadened line widths. Within individual Q-branches the broadening coefficients decreased monotonically with increasing J and for nitrogen broadening varied between 0.19 cm⁻¹ atm⁻¹ at low J and 0.12 cm⁻¹ atm⁻¹ at high J. The corresponding oxygen broadening coefficients were approximately 20% smaller. Self broadening coefficients were also measured for several of the Q-branches and found to be up to ∼4 times higher than the corresponding nitrogen broadening values.     

The 1.58 μm transparency window of methane (6165-6750 cm): Empirical line list and temperature dependence between 80 and 296 K

The empirical line parameters of over 12,000 methane transitions have been obtained at 80 K in the 1.58 μm transparency window (6165-6750 cm⁻¹) which is of importance for planetary applications. This line list (WKC-80K) was constructed from high sensitivity spectra of normal abundance methane recorded by CW-Cavity Ring Down Spectroscopy at low temperature. The minimum intensity reported is on the order of 5×10⁻³⁰ cm/molecule. High resolution Fourier transform spectra have also been recorded using enriched CH₃D samples at 90-120 K in order to facilitate identification of monodeuterated methane features in the methane line list at 80 K. The CH₃D relative contribution in the considered region is observed to be much larger at 80 K than at room temperature. In particular, CH₃D is found dominant in a narrow spectral window near 6300 cm⁻¹ corresponding to the highest transparency region.Using a similar line list constructed at room temperature (Campargue A, Wang L, Liu AW, Hu SM and Kassi S. Empirical line parameters of methane in the 1.63-1.48 μm transparency window by high sensitivity Cavity Ring Down Spectroscopy. Chem Phys 2010;373:203-10.), the low energy values of the transitions observed both at 80 K and at room temperature were derived from the variation of their line intensities. Empirical lower states and J-values have been obtained for 5671 CH₄ and 1572 CH₃D transitions representing the most part of the absorbance in the region. The good quality of these derived energy values is demonstrated by the marked propensity of the corresponding CH₄ lower state J values to be close to integers. The WKC line lists at 80 K and room temperature provided as Supplementary Material allow one accounting for the temperature dependence of methane absorption between these two temperatures. The importance of the 80 K line list for the study of Titan and other methane containing planetary atmospheres is underlined and further improvements are proposed. The resulting information will advance the theoretical modeling of the methane spectrum in the 1.58 μm transparency window.     

Cryogenic absorption cells operating inside a Bruker IFS-125HR: First results for CH4 at 7 μm

New absorption cells designed specifically to achieve stable temperatures down to 66 K inside the sample compartment of an evacuated Bruker IFS-125HR Fourier transform spectrometer (FTS) were developed at Connecticut College and tested at the Jet Propulsion Laboratory (JPL). The temperature stabilized cryogenic cells with path lengths of 24.29 and 20.38 cm were constructed of oxygen free high conductivity (OFHC) copper and fitted with wedged ZnSe windows using vacuum tight indium seals. In operation, the temperature-controlled cooling by a closed-cycle helium refrigerator achieved stability of ±0.01 K. The unwanted absorption features arising from cryodeposits on the cell windows at low temperatures were eliminated by building an internal vacuum shroud box around the cell which significantly minimized the growth of cryodeposits. The effects of vibrations from the closed-cycle helium refrigerator on the FTS spectra were characterized. Using this set up, several high-resolution spectra of methane isotopologues broadened with nitrogen were recorded in the 1200-1800 cm⁻¹ spectral region at various sample temperatures between 79.5 and 296 K. Such data are needed to characterize the temperature dependence of spectral line shapes at low temperatures for remote sensing of outer planets and their moons. Initial analysis of a limited number of spectra in the region of the R(2) manifold of the ν₄ fundamental band of ¹³CH₄ indicated that an empirical power law used for the temperature dependence of the N₂-broadened line widths would fail to fit the observed data in the entire temperature range from 80 to 296 K; instead, it follows a temperature-dependence similar to that reported by Mondelain et al. [17] and [18]. The initial test was very successful proving that a high precision Fourier transform spectrometer with a completely evacuated optical path can be configured for spectroscopic studies at low temperatures relevant to the planetary atmospheres.     

1.55 μm distributed feedback (DFB) lasers subject to strong 1.4 μm optical injection

An experimental analysis of the influence of optical injection at 1.4 μm wavelength into two different commercial 1.55 μm DFB lasers is reported. The results demonstrate the strong dependence of the DFB behaviour on the injection parameters. Complete mode suppression or signal amplification can be obtained by varying the excitation wavelength and/or intensity, suggesting that these devices could be operated as logic ports or signal amplifiers, according to the injected signal.     

The CH3D absorption spectrum in the 1.58 μm transparency window of methane: Empirical line lists at 81 K and 294 K and temperature dependence

In spite of its low isotopic abundance in methane (about 5×10⁻⁴), CH₃D contributes greatly to the very weak absorption in the 1.58 μm methane transparency window. This methane window deserves to be characterized in details because it is important for planetary applications in particular for Titan and the giant planets. In this work, we recorded the CH₃D spectrum by high sensitivity differential absorption spectroscopy (α_min≈5×10⁻⁸ cm⁻¹) both at room temperature and at 81 K. A list of more than 9000 lines was constructed from the 81 K spectrum for the 6099–6530 cm⁻¹ region. In order to get the temperature dependence of the line intensities, the low energy values have to be determined. The rovibrational assignments available in the literature provide low energy values for about 380 strong transitions of the region. This is insufficient to characterize the temperature dependence of the CH₃D absorption between 6200 and 6400 cm⁻¹. In this interval, a list of 5500 lines was constructed from the room temperature spectrum. The empirical energy values of the transitions were derived from the ratio of the intensities at 81 K and 294 K. The exact and empirical lower state energies included in the final line lists provided as Supplementary Material, allow for accounting for the temperature dependence of the CH₃D spectrum in the entire 6099–6530 cm⁻¹ region.Our measurements have been compared to the spectroscopic parameters and assignments available in the literature in particular those adopted in the HITRAN database. Improvements and corrections are proposed for the wavenumber calibration and for some lower state energies.     

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.     

Infrared absorption cross sections for propane (C3H8) in the 3 μm region

Infrared absorption cross sections for propane have been measured in the 3 μm spectral region from spectra recorded using a high-resolution FTIR spectrometer (Bruker IFS 125 HR). The spectra of mixtures of propane 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 and pressures appropriate for atmospheric conditions. Intensities were calibrated using two propane spectra (recorded at 278 and 293 K) taken from the Pacific Northwest National Laboratory (PNNL) IR database.     

6.2 W laser-diode end-pumped continuous-wave Nd:YALO3 laser at 1.34 μm

We report a compact and efficient LD end-pumped linearly polarized Nd:YAP laser operating at 1.34 μm. The laser system with different crystal lengths, output couplers and cavity types were compared. Based on optimizing of the pump system and laser cavity, 6.2 W laser radiation at 1341.4 nm with c-axis polarized was achieved, corresponding to an optical conversion efficiency of about 24.8% with respect to the incident pump power. The laser threshold was only about 1.3 W and the optical slope efficiency was up to 27.2%.     

Self-broadening coefficients and positions of acetylene around 1.533 μm studied by high-resolution diode laser absorption spectrometry

The self-broadening coefficients of acetylene at room temperature have been measured for 10 lines in the P branch of the bands of ¹²C₂H₂ and ¹³C¹²CH₂ near 1.533 μm, using a high resolution tunable diode laser spectrometer developed for the Martian space mission PHOBOS-Grunt. The collisional widths are obtained by fitting each recorded line with the Voigt profile as well as the Rautian profile accounting for the collisional Dicke narrowing effect. The standard Voigt model provides slightly smaller broadening coefficients than the Rautian model. Our data are thoroughly compared to the main atmospheric molecule database HITRAN and previous values in various bands of acetylene. Moreover, it is worth noting that a large number of new transitions not listed in the latest HITRAN08 were measured and identified for the first time.     

Absolute, high resolution water transpiration rate measurements on single plant leaves via tunable diode laser absorption spectroscopy (TDLAS) at 1.37 μm

A new sampling-free and calibration-free multi-channel hygrometer using near infrared (NIR) tunable diode laser absorption spectroscopy (TDLAS) at 1.37 μm was developed and used to determine absolute transpiration rates of single plant leafs. Four 8×6× 4 cm³, fiber-coupled absorption cells are used to simultaneously measure absolute water vapor concentrations with an absolute accuracy of about 5% and a temporal resolution of about 2 s. Two chambers (BOTTOM, TOP) are directly attached to the leaf surface, while two chambers (IN, OUT) analyze the purge gas supplied to the plant leaf and the total outflow of the leaf chambers. The BOTTOM–TOP comparison provided a direct, leaf-side resolved ratio of stomatal conductance and–by taking into account the purge gas flow and the leaf area exposed–leaf side resolved water transpiration rates. The OUT–IN-difference yielded the total leaf transpiration rate with 2 μmol/m²/s resolution. The new multi-point hygrometer was validated by monitoring of the transpiration dynamics of a plant of the species Epipremnum pinnatum (L.) Engl. during diurnal variation of the leaf irradiation. During these experiments the differential H₂O concentration resolution between two chambers was determined to be better than 3 ppm at Δt= 2 s (i.e. better than 711 ppb m Hz^1/2). This performance was verified by an Allan analysis over a 30 min time period using CH₄ as a surrogate absorber and yielded an average optimum optical resolution of 4.9×10^-6 for 83 s measurement time, i.e. a CH₄ resolution of 892 ppb, which corresponds to the optical resolution needed for a water sensitivity of 454 ppb m Hz^1/2. PACS  07.57.Ty; 42.62.Fi; 42.62.Be; 42.55.Px; 82.80.Gk     

High sensitivity CW-cavity ring down spectroscopy of N2O near 1.5 μm (III)

We present the third part of the investigation of the high sensitivity absorption spectrum of nitrous oxide by CW-Cavity Ring Down Spectroscopy near 1.5 μm. In the two first contributions (A. Liu, et al., J. Mol. Spectrosc. 244 (2007) 33-47 and A. Liu, et al., J. Mol. Spectrosc. 244 (2007) 48-62) devoted to the 5905-6833 cm⁻¹ region, more than 9000 line positions of five isotopologues (¹⁴N₂¹⁶O, ¹⁵N¹⁴N¹⁶O, ¹⁴N¹⁵N¹⁶O, ¹⁴N₂¹⁷O and ¹⁴N₂¹⁸O), were rovibrationally assigned to a total of 115 bands, most of them being newly detected. The achieved sensitivity (α_min∼3 × 10⁻¹⁰ cm⁻¹) allowed for the detection of lines with intensity weaker than 2 × 10⁻²⁹ cm/molecule. In this contribution, the investigated region was extended up to 7066 cm⁻¹. The analysis based on the predictions of the effective Hamiltonian model has allowed assigning about 1500 transitions to 17, 1, 2 and 1 bands of the ¹⁴N₂¹⁶O, ¹⁴N¹⁵N¹⁶O, ¹⁵N¹⁴N¹⁶O and ¹⁴N₂¹⁸O isotopologues, respectively. Eleven of these 21 bands are newly reported, while the observations of the transitions are extended to higher J values for most of the others. The band by band analysis has allowed reproducing the measured line positions within the experimental uncertainty (about 1 × 10⁻³ cm⁻¹) and determining the corresponding spectroscopic parameters. A detailed analysis of the rovibrational perturbations affecting three bands of ¹⁴N₂¹⁶O is presented.