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.     

Analysis of the D2O absorption spectrum near 2.5 μm

The D₂O absorption spectrum recorded with a selective modulation Girard spectrometer in the region of 3690–4190 cm⁻¹ (resolution ∼0.07 cm⁻¹) has been analyzed. Based on the fitting of experimental data the spectroscopic parameters of the vibrational state (011) have been determined and the parameters of the vibrational states (110) and (030) have been estimated.     

Laser-photoacoustic spectroscopy of water-vapor continuum and line absorption in the 8 to 14 μm atmospheric window

This is a comprehensive study of water-vapor line and continuum absorption in the 8–14μm atmospheric window by laser-photoacoustic spectroscopy. The characteristics of laser-photoacoustic spectroscopy and detectors are discussed with results on continuum and line absorption at selected CO₂-laser wavelengths.We have assigned four weak absorption lines which occur at the CO₂-laser emissions 10P(40), 10R(20), 9P(38) and 9R(36) to pure rotational transitions of H₂O, and have determined the dependence of the continuum water-vapor absorption over the temperature range +70°C and −20°C. The measured negative temperature coefficient of the continuum is consistent with both monomer and dimer models, yet not with predictions of larger water clusters.Experiments with supersaturated water vapor indicate that for S ⩾ 1 collision broadening of distant strong lines as well as water dimer absorption contribute to the continuum. However, the dimer absorption is an order of magnitude too small to cause a significant contribution at ambient atmospheric conditions.We have investigated the effect of UV-radiation on the 8–14μm absorption of water vapor, buffered either with N₂ or synthetic air. The observed changes are explained by UV-photodissociation of H₂O molecules and by ozone production. There is no evidence in favor of a cluster model.Finally, we compared our measured spectra with LOWTRAN 6 and HITRAN models. The LOWTRAN yields a stronger negative temperature dependence than observed while the HITRAN does not predict the observed continuum absorption.     

Dual-beam laser heterodyne spectrometer: Ethylene absorption spectrum in the 10 μm range

A laser heterodyne spectrometer for the 10 m region has been built. A 5 MHz apparatus function is obtained. The improvement of this spectrometer using a dual-beam technique is described. The folding effects in heterodyne spectroscopy are discussed. The recorded lineshapes are explained. An ethylene spectrum is shown as an example.     

The infrared spectrum of HCCF around 17 μm

The absorption spectrum of HCCF in the region of the CH bending fundamental ν₄ has been studied at a resolution of about 0.03 cm^?1. In addition to the fundamental, the rotational analysis has been performed for six “hot” bands. Several molecular parameters have been derived. The effects of l-type resonances have been discussed. In particular, the influence of the resonance between the sublevels of ν₄ + ν₅ on the effective centrifugal distortion constants has been investigated.     

The absorption spectrum of H2 18O in the range 13400–14460 cm?1

Using a Fourier-transform spectrometer, we have measured the absorption spectrum of H₂ ¹⁸O vapor in the range 13400?C14460 cm^?1 at room temperature with a resolution of 0.03 cm^?1 and a threshold sensitivity in absorption of 10^?6 cm^?1. With a multipass cell, the volume of which was 3 L and the base of which was 25 cm, a length of the absorbing layer of 10 m has been achieved. A high signal-to-noise ratio, on the order of 1000, has allowed us to detect about 700 lines of the H₂ ¹⁸O molecule, the intensities of which were as low as 10^?25 cm/molecule, at 296 K. The observed lines have been attributed to eleven vibrational-rotational bands of the molecule.     

Optical properties of aluminum dodecaboride (α-AlB12) in the region of the transparency window

The absorption coefficient of α-AlB₁₂ was measured on single crystal samples at T=300 K within a broad spectral region (0.6–25 μm). In the region of the transparency window (3–6 μm), the absorption coefficient was measured in the temperature range from 165 to 650 K. An analysis of the experimental data shows that the energy spectrum of local states in the α-AlB₁₂ bandgap has certain features. It was established that a broad band of local states lies near the conduction band and that a trap level is located at 0.11±0.02 eV from the top of the valence band. __________ Translated from Fizika Tverdogo Tela, Vol. 43, No. 9, 2001, pp. 1573–1574. Original Russian Text Copyright ? 2001 by Zaitsev, Fedorov, Golikova, Orlov. Deceased.     

Frequency measurements in the 10 μm spectrum of 11BCl3

This paper presents a study of the spectroscopy of ¹¹BCl₃ using the Doppler-free saturated absorption technique. Many lines in the degenerate ν₃ fundamental of this molecule have been recorded using the 10P branch of a carbon dioxide laser. The absolute frequencies of the linecentres of these absorptions have been measured to an accuracy of better than 10 kHz, using frequencies calibrated against transitions in SF₆ and OsO₄. Hyperfine structure due to the Cl nuclei was easily resolved, and more detailed structure, which may be attributed to the ¹¹B quadrupole interaction, was also seen. The splittings between individual quadrupole components were measured to an accuracy of better than 2 kHz where SF₆ references were used, and to about 8 kHz in the case of OsO₄. Peak-to-peak linewidths as low as 22 kHz have been recorded, representing the highest resolution data yet obtained for this molecule.     

Superfluorescent fiber source at 3.9 μm in the attenuation minimum of the atmospheric window 3–5 μm

Superfluorescence has been demonstrated for the first time at 3.9m in holmium-doped fluoride glass optical fiber. Fluorescence measurements were possible at room temperature while pumping around 650 nm. Cooled to 173 K superfluorescence was obtained.     

The near infrared (0.8−2.6µm) absorption spectrum of a dense sodium vapor and possible mechanisms of the spectrum formation

The absorption coefficient of a dense sodium vapor (N₀ ～ 10¹⁷–10¹⁸ cm^{? 3}) in the near infrared spectral range (0.8–2.6 µm) was measured in a homogeneously heated isolated cell. In the range of parameters studied, the sample exhibits significant absorption. Neither the observed spectral features nor the measured absorption coefficients can be explained using the existing notions of the possible absorption mechanisms (absorption due to a forbidden intercombination transition, collision-induced processes, the trimer vapor component, and many-particle effects) and the available data.     

Shift of the centers of H<Subscript>2</Subscript>O absorption lines in the region of 1.06 μm

The shift coefficients for the lines of the ν₁ + ν₂ + ν₃ and ν₂ + 2ν₃ bands of H₂O in the region from 9403 to 9413 cm^?1 are measured and calculated. The measurements are performed using an intracavity laser spectrometer based on a neodymium laser with a determination error of the line center of 0.003–0.004 cm^?1. The Ar, Kr, and Xe noble gases, as well as nitrogen, oxygen, and hydrogen were used as buffer gases. The coefficients of shifts in eight H₂O absorption lines induced by oxygen, nitrogen, and atmospheric air pressures fall into the region from ?0.004 to ?0.069 cm^?1/bar. The calculations are performed by a semiempirical method using variational wave functions, which, in contrast to other studies, correctly takes into account intramolecular interactions. The calculated values agree satisfactorily with experimental data.     

ICLAS of water in the 770 nm transparency window (12 746–13 558 cm−1). Comparison with current experimental and calculated databases

The absorption spectrum of water vapor has been investigated by intracavity laser spectroscopy (ICLAS) in the 12 746–13 558 cm^?1 spectral region corresponding to an interesting transparency window of the atmosphere, partly obscured by the A band of molecular oxygen.The achieved sensitivity—in the order of α_min～10^?9 cm^?1—has allowed one to measure 1062 water lines with intensities ranging from 1.6×10^?28 to 2.35×10^?24 cm/molecule at 296 K. A total of 169 new and improved energy levels belonging to 21 vibrational states could be determined from 374 newly measured transitions. The retrieved experimental line list is compared with the spectra calculated by Schwenke and Partridge, and Barber and Tennyson. Comparison with the available experimental databases shows that the obtained results represent a significant improvement of the knowledge of the water absorption in the considered region, in particular in the region of the oxygen A band.     

The absorption spectrum of 12C2D2 in the 10000–12500 cm−1 spectral region

The absorption spectrum of dideuteroacetylene has been recorded by intracavity laser absorption spectroscopy (ICLAS) in the 10 200–12 500cm^?1 spectral region. Among 25 absorption bands of ¹²C₂D₂ rotationally analysed in this spectral region, 17 are newly observed. They include one II_u-Σ⁺ _g and thirteen Σ⁺ _u-Σ⁺ _g bands starting from the vibrational ground state and eleven hot bands from the V ₄ = 1 and V ₅ = 1 lower states. The rotational structure of two excited levels is affected by a strongly J-dependent interaction with a perturber which induces intensity transfer to extra lines. The coupling is identified as a I-resonance interaction with δ_u dark states and the vibrational assignment of the perturbers is discussed. Two Σ-Σ bands of the ¹²C¹³ CD₂ species, present in natural abundance in the sample, could also be identified and rotationally analysed. Most of the corresponding excited vibrational levels of ¹²C₂D₂ were unambiguously assigned using the polyad model [Herman, M., el idrissi, M. I., Pisarchik, A., Campargue, A., Gaillot, A.-C., Biennier, L., di lonardo, G. and Fusina, L., 1998, J. chem. Phys., 108, 1377] which allows vibrational energies and B _V rotational constants to be predicted. In particular the previously highlighted 1/244 anharmonic resonance is confirmed by energy and intensity features in several {(V ₁, V ₂, V ₃, V ₄ = 0, V ₅ = 0),(V ₁ ?1, V ₂ + 1, V ₃ V ₄ = 2, V ₅ = 0)} dyads. Significant deviations between predicted and experimental energy levels are observed for a few levels and discussed.     

Impact of water vapor on 1.51 μm ammonia absorption features used in trace gas sensing applications

Water-vapor-induced pressure broadening is reported for two NH₃ absorption features at 6612.7 and 6596.4 cm⁻¹ that are exploitable for gas sensing applications at atmospheric pressure. Absorption spectra of different NH₃–H₂O–N₂ mixtures were measured at an elevated temperature of 70°C to enable high H₂O concentrations to be reached. Line parameters were determined from a fitting procedure. The significantly greater values obtained for the H₂O-broadening coefficients of the two lines compared to N₂-broadening leads to cross-sensitivity effects in NH₃ trace gas sensors based on spectroscopic techniques that are sensitive to the width of the analyzed absorption line, as is the case in a simple implementation of wavelength modulation spectroscopy or in photoacoustic spectroscopy. In such a case, cross-sensitivity results in inaccurate gas concentration retrieval when the composition of the diluting gas changes. H₂O represents a potentially significant cross-sensitivity source as its concentration may be subject to large variations, especially in high-temperature applications where concentrations up to a couple of tens of percent may be encountered. In contrast to interference which can be minimized by an appropriate choice of the analyzed transitions, cross-sensitivity affects the entire spectrum of the analyte and is thus unavoidable in the mentioned type of gas sensors.     

The refractivity of CO2 gas in the region of 10 μm

The refractivity of the CO₂ gas is measured with an experimental error of 2% in the 10-m region, using 10.4-m band CO₂ laser line. The frequency of the CO₂ laser is swept through the Doppler profile of the laser line. The experiment is achieved using a 0.63-m He–Ne/10.6-m CO₂-laser interferometer with a 2-m long vacuum cell. From the result, it is found that the Koch's formula also holds for the wavelengths in the 10-m region within an accuracy of 2%.     

Nature of the temperature dependence of the absorption coefficient in the remote wing of the 4.3 μm CO2 band

The complex nature of the temperature dependence of the absorption coefficient beyond the edge of the CO₂ 4.3 m band — the change of the sign of the derivative of the absorption coefficient with respect to the temperature near the edge and in the remote wing of the band — is explained on the basis of the theory of spectrum line wings. The first change in the sign is due to the temperature dependence of the classical potential of intermolecular interaction; the second depends mainly on the difference in the quantum energies of molecule interaction. Therefore, a study of the dependence of the absorption coefficient on the temperature in the band wings provides information about the nature of the terms of the interacting molecules.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 12, pp. 42–45, December, 1987.     

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.     

Line coupling in the temperature and frequency dependences of absorption in the microwindows of the 4.3 μm CO2 band

The shapes of the self- and N₂-broadened ν₃CO₂ fundamental vibration-rotation band in the microwindows (troughs between the lines) have been measured at various temperatures. Important deviations with respect to the superposition of Lorentzian profiles are observed. These deviations are interpreted in terms of line coupling, which redistributes the intensity in the whole band. In order to take into account this line coupling, two models are considered within the frame of the impact theory. The first model uses the strong-collision approximation to describe the rotational energy transferred by collisions. It leads to a simple analytical expression for the band profile. The second model is based on the exponential-gap law. These two models account well for the frequency dependence of the measured absorption in the microwindows and for the temperature dependence in the case of the N₂-broadened CO₂ band but not in the self-broadened case. The influence of the line-coupling rotational distribution, which differs significantly in the two models, is discussed. The possible role of the finite duration of collision in rotational energy transfer is examined.     

Absorption spectrum of HDO in the 1.06 μm region at a temperature of 1000 K

In the 9387–9450 cm^–1 region at temperatures of 300–1000 K, we have used an intracavity laser spectrometer based on a neodymium laser with threshold sensitivity to absorption 10^–8 cm^–1 and spectral resolution 0.035 cm^–1 to study the absorption spectrum of D₂¹⁶O, H₂¹⁶O, and HD¹⁶O vapor. The high-temperature spectrum contains more than 450 absorption lines, 240 of which are assigned to the HDO isotopomer. The absorption lines of HDO were identified and belong to nine vibrational transitions: 3ν₂ +ν₃, 2ν₁ + 3ν₂, 2ν₁ + ν₃, 4ν₂ + ν₃, 7ν₂, ν₁ + 2ν₂ + ν₃, ν₁ + 5ν₂, ν₁ + 2ν₂, and 3ν₃ – ν₂.