Infrared and far-infrared spectroscopy of CH3OH: TeraHertz laser lines and assignments

We use a ¹³CO₂ laser as optical pumping source to search for new THz laser lines generated from ¹³CH₃OH. Nineteen new THz laser lines (also identified as far-infrared, FIR) ranging from 42.3 μm (7.1 THz) to 717.7 μm (0.42 THz) are reported. They are characterized in wavelength, offset, relative polarization, relative intensity, and optimum working pressure. We have assigned eight laser lines to specific rotational energy levels in the excited state associated with the C-O stretching mode.     

Synthesis of optical standard frequencies in the S, C and L telecommunication bands by use of four-wave mixing in semiconductor optical amplifiers

The generation of standard reference frequencies close to the ITU channels is essential for the calibration and maintenance of DWDM systems. This work describes a method to synthesize frequency references in the range from 187.1 to 205.1 THz (1462-1602 nm). The method is based on the generation of four equispaced frequencies (by the process of four-wave mixing in a semiconductor amplifier) of which two are locked to absorption lines of the acetylene ¹²C₂H₂ (1511-1542 nm).     

Line shift and mixing in the ν4 and 2ν2 band of NH3 perturbed by H2 and Ar

Pressure induced line shift and line mixing parameters have been measured for 66 rovibrational lines in the ν₄ band and for 10 lines in the 2ν₂ band of NH₃ perturbed by H₂ and Ar at room temperature (T = 296 K). These lines with J values ranging from 2 to 10 are located in the spectral range 1450-1600 cm⁻¹. Experiments were made with a high-resolution Fourier transform spectrometer. The line shifts and line mixing parameters have been derived from the non-linear least-square multi-pressure fitting technique. The shift coefficients are compared with those calculated from the Robert-Bonamy formalism (RB). The results are generally in satisfactory agreement with the experimental data.     

New measurements of the water vapor continuum in the region from 0.3 to 2.7 THz

We present a spectroscopic study of the water vapor continuum absorption in the far-IR region from 10 to 90 cm⁻¹ (0.3-2.7 THz). The experimental technique combines a temperature-stabilized multipass absorption cell, a polarizing (Martin-Puplett) interferometric spectrometer, and a liquid-He-cooled bolometer detector. The contributions to the absorbance resulting from the structureless H₂O-H₂O and H₂O-N₂ continua have been measured in the temperature range from 293 to 333 K with spectral resolution of 0.04-0.12 cm⁻¹. The resonant water vapor spectrum was modeled using the HITRAN04 database and a Van Vleck-Weisskopf lineshape function with a 100 cm⁻¹ far-wing cut-off. Within experimental uncertainty, both the H₂O-H₂O and H₂O-N₂ continua demonstrate nearly quadratic dependencies of absorbance on frequency with, however, some deviation near the 2.5 THz window. The absorption coefficients of 3.83 and 0.185 (dB/km)/(kPa THz)² were measured for self- and foreign-gas continuum, respectively. The corresponding temperature exponents were found to be 8.8 and 5.7. The theoretically predicted foreign continuum is presented and a reasonable agreement with experiment is obtained.     

High sensitivity CW-cavity ring down spectroscopy of water in the region of the 1.5 μm atmospheric window

The absorption spectrum of natural water vapour around 1.5 μm has been recorded with a typical sensitivity of 5 × 10⁻¹⁰ cm⁻¹ by using a CW-cavity ring down spectroscopy set up based on fibred DFB lasers. A series of 31 DFB lasers has allowed a full coverage of the 6130.8-6748.5 cm⁻¹ (1.63-1.48 μm) region corresponding to the H transparency band of the atmosphere. The line parameters (wavenumber and intensity) of a total of 5190 lines, including 4247 lines of water vapor, were derived by a one by one fit of the lines to a Voigt profile. Different isotopologues of water (H₂¹⁶O, H₂¹⁸O, H₂¹⁷O, and HD¹⁶O) present in natural abundance in the sample contribute to the spectrum. For the main isotopologue, H₂¹⁶O, 2130 lines were measured with line intensities as weak as 10⁻²⁹ cm/molecule while only 926 lines (including a proportion of 30% inaccurate calculated lines) with a minimum intensity of 3 × 10⁻²⁷ cm/molecule are provided by the HITRAN and GEISA databases. Our comparison in the whole 5750-7965 cm⁻¹ region, has also evidenced that an error in the process of conversion of the intensity units from cm⁻²/atm to cm⁻¹/(molecule × cm⁻²) at 296 K, has led to H₂¹⁶O line intensities values listed in the HITRAN-2000 database, systematically 8 % below the original FTS values. The rovibrational assignment was performed on the basis of the ab initio calculations by Schwenke and Partridge with a subsequent refinement and validation using the Ritz combination principle together with all previously measured water transitions relevant to this study. This procedure allowed determining 172, 139, 71, and 115 new energy levels for the H₂¹⁶O, H₂¹⁸O, H₂¹⁷O, and HD¹⁶O isotopologues, respectively. The results are compared with the available databases and discussed in regard of previous investigations by Fourier transform spectroscopy. The spectrum analysis has showed that most of the transitions which cannot be assigned to water are very weak and are due to impurities such as carbon dioxide and ammonia, leaving only about 3% of the observed transitions unassigned. The interest of a detailed knowledge of water absorption for trace detectors developed in the 1.5 μm range is underlined: for instance HDO contributes significantly to the considered spectrum while no HDO line parameters are provided by the HITRAN database.     

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.     

Silicon donor and Stokes terahertz lasers

Two types of lasers based on hydrogen-like impurity-related transitions in bulk silicon operate at frequencies between 1 and 7 THz (wavelength range of 50-230 μm). These lasers operate under mid-infrared optical pumping of n-doped silicon crystals at low temperatures (<30 K). Dipole-allowed optical transitions between particular excited states of group-V substitutional donors are utilized in the first type of terahertz silicon lasers. These lasers have a gain ∼1-3 cm⁻¹ above the laser thresholds (>1 kW cm⁻²) and provide 10 ps-1 μs pulses with a few mW output power on discrete lines. Raman-type Stokes stimulated emission in the range 4.6-5.8 THz has been observed from silicon crystals doped by antimony and phosphorus donors when optically excited by radiation from a tunable infrared free electron laser. The scattering occurs on the 1s(E)→1s(A₁) donor electronic transition accompanied by an emission of the intervalley transverse acoustic g-phonon. The Stokes lasing has a peak power of a few tenths of a mW and a pulse width of a few ns. The Raman optical gain is about 7.4 cm GW⁻¹ and the optical threshold intensity is ∼100 kW cm⁻².     

Accurate rotational spectroscopy of sulfur dioxide, SO2, in its ground vibrational and first excited bending states, v2 = 0, 1, up to 2 THz

Approximately 150 pure rotational transitions each have been recorded for SO₂, v₂ = 0 and 1, in selected frequency regions up to 2 THz. The J and K_a quantum numbers reach very high values: 92 and 23, respectively, for the ground vibrational state and 81 and 21, respectively, for the first excited bending state. The highest levels accessed are almost 3000 cm⁻¹ above ground. The relative experimental uncertainties Δν/ν are about 10⁻⁸ for several medium to strong, isolated lines, and generally better than 2.5 × 10⁻⁷. Improved spectroscopic parameters have been obtained for both states, particularly for the excited bending state. In fact, the accuracies with which the energy levels of the v₂ = 1 state are known depend essentially only on the accuracy with which the vibrational spacing is known from infrared spectroscopy.     

High power room-temperature design of terahertz quantum cascade laser based on difference frequency generation

Terahertz (THz) quantum cascade lasers (QCLs) are key elements for high-power terahertz beam generation for integrated applications. In this study, we design a highly nonlinear THz-QCL active region in order to increase the output power of the device especially at lower THz frequencies based on difference frequency generation (DFG) process. It has been shown that the output power increases for a 3.2 THz structure up to 1.2 μW at room temperature in comparison with the reported power of P = 0.3 μW in [1]. The mid-IR wavelengths associated with this laser are λ₁ = 12.12 μm and λ₂ = 13.93 μm, which are mixed in a medium with high second-order nonlinearity. A similar approach has been used to design an active region with THz frequency of 1.8 THz. The output power of this structure reaches to 1 μW at room temperature where the mid-IR wavelengths are λ₁ = 12.05 μm, λ₂ = 12.99 μm.     

Pressure shift and broadening of 110-101 water vapor lines by atmosphere gases

This paper is devoted to the measurement of pressure shift and broadening parameters of water-vapor lines of the pure rotational transition 1₁₀-1₀₁ in the ground vibrational state of H₂¹⁶O at 556.936 GHz, H₂¹⁷O at 552.02 GHz, H₂¹⁸O at 547.676 GHz, and the vibrationally excited state v₂=1 line of H₂¹⁶O at 658.003 GHz. The broadening coefficients of the line at 556.936 GHz (for N₂ and O₂ as perturbing gases) coincide within the errors with the values obtained recently by Seta et al. [Pressure broadening coefficients of the water vapor lines at 556.936 and 752.033 GHz. JQSRT 2008;109:144-50] by means of a very different technique (THz-TDS). Pressure shift and broadening for other lines were measured for the first time. Comparison of our results with previous measurements and theoretical calculations is presented.     

Reinvestigation of pressure broadening parameters at 60-GHz band and single 118.75 GHz oxygen lines at room temperature

Low pressure measurements of broadening parameters of the 118.75 GHz fine structure line of oxygen molecule have been made by a BWO-based spectrometer with acoustic detector (RAD) at room temperature. Pressure broadening parameters were obtained for the buffer gases O₂, N₂, Ne, He, Ar, H₂O, CO₂, and CO and have the following values 2.23 ± 0.01, 2.245 ± 0.02, 1.375 ± 0.02, 1.62 ± 0.03, 2.005 ± 0.02, 2.52 ± 0.04, 2.66 ± 0.08, and 2.31 ± 0.05 MHz/Torr, respectively. Measured central frequency is 118 750.340 ± 0.007 MHz. The central frequencies and broadenings by O₂ and N₂ of fine structure lines 1⁺, 5⁻, 7⁺, 11⁺, and 15⁻ belonging to the 60-GHz band are also measured. Comparison of previous and recent data on electronic, rotational, and fine structure lines broadenings reveals their close values (within 10%) and dependencies on corresponding rotational quantum numbers for these different oxygen spectra stretching from millimeter through submillimeter up to the optical bands. Such similarity could be used for estimation of the broadenings of not measured yet oxygen lines.     

Observation of nonstationary effects in saturation spectroscopy

We have studied the nonstationary effects in saturated absorption spectroscopy of the ⁸⁷Rb D₂ line. Varying the size of the σ⁺ polarized pump laser beam, we observed saturated absorption spectra for the σ^± polarized probe beam. For equal polarizations of the pump and probe beams, we found that the resonance signal for the F_g = 1 → F_e = 2 line, and the crossover lines between F_g = 1 → F_e = 2 and F_g = 1 → F_e = 1 (and 0) lines increased to a greater extent than the others. This observation can be understood from the calculated time evolution of the populations of the ground-state sublevels by means of a rate equation model. We also compared experimental data for other conditions with the calculated results. We found good agreement between the calculated results and the data.     

N2- and O2-broadening of CO2 for the (301)III ← (000) band at 6231 cm

The N₂- and O₂-broadening effect have been investigated for 10 absorption lines of the CO₂ (30⁰1)_III ← (00⁰0) band centered at 6231 cm⁻¹, in the range from P(28) to R(28) by a near-infrared diode-laser spectrometer. We have analyzed the observed line profiles with the Galatry function, and determined the N₂- and O₂-broadening coefficients precisely. The air-broadening coefficients for these lines have been derived. The present results are compared with those of the previous studies for this band and with some of the other bands.     

Extended THz measurements of nitrous oxide, N2O

High precision measurements of the atmospheric trace gas nitrous oxide have been extended up through 1.5 THz. The data set includes ground state, ν₂, 2ν₂, ¹⁵NNO, N¹⁵NO, and N₂¹⁸O spectra up to J = 68. Improved Hamiltonian parameters are given.     

CH<Subscript>3</Subscript>OH optically pumped by a <Superscript>13</Superscript>CO<Subscript>2</Subscript> laser: new laser lines and assignments

We report 12 new THz (far-infrared) laser lines from methanol (CH₃OH), ranging from 58.1 μm (5.2 THz) to 624.6 μm (0.5 THz). A ¹³CO₂ laser of wide tunability (110 MHz) has been used for optical pumping, allowing access to previously unexplored spectral regions. Optoacoustic absorption spectra were used as a guide to search for new THz laser lines, which have been characterized in wavelength, polarization, offset, relative intensity, and optimum operation pressure. For 20 laser lines previously observed, we have measured the absorption offset with respect to the ¹³CO₂ laser line center. PACS 33.20.Ea; 33.20.Vq; 33.80.-b     

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.     

Ar-Broadening of isotropic Raman lines in the ν2 band of acetylene

Using a high resolution Raman spectrometer, we have measured Ar-broadening coefficients in the ν₂Q branch of C₂H₂ for 22 lines at 295 K, 20 lines at 174 K, and 16 lines at 134 K. These lines with J values ranging from 1 to 23 are located in the spectral range 1970.9-1974.3 cm⁻¹. The collisional widths are obtained by fitting each spectral line with a Rautian profile. The resulting broadening coefficients are compared with theoretical values arising from close coupling and coupled states calculations. A satisfactory agreement is obtained at room as well as at low temperatures, especially for odd J lines. By comparing broadening coefficients at 295, 174, and 134 K from a simple power law, the temperature dependence of these broadenings has been determined both experimentally, and theoretically.     

The cavity-enhanced absorption spectrum of NH3 in the near-infrared region between 6850 and 7000 cm

In this paper, we describe new high-resolution measurements of the absorption spectrum of ¹⁴NH₃ in the 6850-7000 cm⁻¹ region using cavity-enhanced absorption spectroscopy (CEAS), and Fourier-transform spectroscopy (FTS) between ∼6400 and 6900 cm⁻¹. The CEAS measurements were used to determine line positions, line intensities (cross-sections) and pressure-broadening parameters, the latter in three different bath gases. A total of 1117 NH₃ lines were observed. The accuracy of the line positions is about 0.001 cm⁻¹, and absorptions cross-sections as low as 1×10⁻²³ cm² molecule⁻¹ are reported.     

Absorption spectra of CO2 and CO2 near 1.05 μm

The absolute line intensities of the Fermi triad 2003i-00001 (i = 1, 2, 3) of ¹²C¹⁶O₂ and ¹³C¹⁶O₂ isotopic species of carbon dioxide were retrieved from Fourier-transform spectra recorded at Doppler limited resolution in the region 9200-9700 cm⁻¹. The accuracy of the line intensity determination is estimated to be better than 15% for most lines. The vibrational transition dipole moments squared and Herman-Wallis coefficients have been determined. The global fittings of the observed line intensities within the framework of the effective operators method have been performed. The fitting results reproduce the data within experimental uncertainty.     

HDO absorption spectrum above 11 500 cm: Assignment and dynamics

Assignment of an HDO line list extracted from a recently measured H₂O/HDO/D₂O Fourier transform absorption spectrum recorded in the 11 600-23 000 cm⁻¹ region by Bach et al. (M. Bach, S. Fally, P.-F. Coheur, M. Carleer, A. Jenouvrier, A.C. Vandaele, J. Mol. Spectrosc. 232 (2005) 341-350.) is presented. More than 94% of the 3256 lines are given quantum number assignments and ascribed to line absorption by HDO; most of the remaining lines are actually due to D₂O. High accuracy variational predictions of line positions and intensities are used for the spectral assignment process. Assignments to the ν₁ + 5ν₃, 2ν₂ + 5ν₃, ν₁ + ν₂ + 3ν₃ and ν₁ + 6ν₃ bands are presented for the first time. Comparisons are made with published ICLAS spectra covering the same spectral region and suggestions made for its recalibration. The results are used to illustrate the dynamical behaviour of highly excited vibrational states of HDO and to discuss previous vibrational assignments to high lying rotation-vibration states of this system.