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.     

First assignment of the 5ν4 and ν2+4ν4 band systems of CH4 in the 6287-6550 cm region

This paper reports the first assignment of rovibrational transitions of the 5ν₄ and ν₂+4ν₄ band systems of ¹²CH₄ in the 6287-6550 cm⁻¹ region, which is usually referred to as part of the 1.58 μm methane transparency window. The analysis was based on two line lists previously obtained in Grenoble by cavity ring down spectroscopy at T=297 and 79 K completed by three long-path Fourier transform spectra recorded in Reims (at 290 K, L=1603 m, P=1-34 mbar). In order to determine the dipole transition moment parameters and quantify the intensity borrowing due to the resonance interactions, we had to include in the fit of the effective Hamiltonian model some lines of the stronger ν₁+3ν₄ and ν₂+4ν₄ bands. For this purpose, intensities of 179 additional lines were retrieved from FTS spectra above 6550 cm⁻¹ though the analysis of these higher bands is not complete. About 1955 experimental line positions and 1462 line intensities were fitted with RMS standard deviations of 0.003 cm⁻¹ and 13.1%, respectively. A line list of 8029 calculated and observed transitions which are considered as dominant was constructed for ¹²CH₄ in the 6287-6550 cm⁻¹ region. This is the first high-resolution analysis and modelling of 5-quanta band systems of ¹²CH₄.     

High-resolution infrared spectroscopy of the interacting ν9, ν5 + ν6 and 3ν6 levels of CH2BrF

The high-resolution (0.0030 cm⁻¹) Fourier transform infrared spectrum of CH₂⁷⁹BrF has been studied in part of the atmospheric window between 910 and 980 cm⁻¹, the region of the ν₉ (935.847 cm⁻¹) and ν₅ + ν₆ (961.239 cm⁻¹) bands. The ν₉ fundamental consists of a pseudo a-type band induced by Coriolis coupling with ν₅ + ν₆, in turn exhibiting a predominant a-type structure. Several interactions connecting these levels and the dark state 3ν₆ have been assessed. The whole data set is treated using Watson’s A-reduced Hamiltonian in the I^r representation implemented with first order a- and b- and c-type Coriolis terms. A detailed analysis of the rotational structure yields a set of accurate upper-state parameters up to quartic distortion terms for ν₉ and ν₅ + ν₆. In addition, spectroscopic information about the dark ternary overtone of ν₆ has been obtained.     

High resolution infrared spectrum and global analysis of ν5, ν12, and ν12 + ν6 − ν6 in CH3SiH3

The vibration-torsion-rotation spectrum of CH₃SiH₃ has been measured from 470 to 725 cm⁻¹ at near-Doppler resolution. The full-width at half - maximum of the lines observed near 600 cm⁻¹ was 0.0011 cm⁻¹. The spectra were obtained using a Bruker IFS 125 HR Fourier transform spectrometer with the broadband source radiation being supplied from the synchrotron emission of the storage ring at the Canadian Light Source. Three vibrational bands were investigated: the lowest lying perpendicular fundamental ν₁₂ centred near 524 cm⁻¹, the lowest lying parallel fundamental ν₅ near 703 cm⁻¹, and the torsional hot band ν₁₂ + ν₆ − ν₆ near 534 cm⁻¹. For ν₁₂ and ν₅, the resolution and sensitivity are much improved over those in earlier studies, with many of the torsional multiplets now being resolved even in the cases where the upper levels are unperturbed. The primary motivation for the present work was the hot band, here reported for the first time, where the dependence of the silyl rock in ν₁₂ on the torsional motion is much more pronounced. In addition, for the vibrational ground state (gs), two “forbidden” high torsional overtones v₆ = 3 ← 0 and 5 ← 0 have been observed that become allowed through resonant mixing of the upper states with ν₁₂ and ν₅, respectively. In each case, two (K, σ) series have been measured where the mixing is largest. Here σ = 0, 1, −1 labels the torsional sub-levels. Using the Fourier transform waveguide spectrometer at E. T. H., the three σ-components of the (J = 1 ← 0) transition in ν₁₂ + ν₆ were observed, and a series of direct l-doubling transitions in ν₁₂ + ν₆ were measured for σ = 0. In a global fit, all the new data have been analysed along with the frequencies for other transitions obtained in earlier investigations. The analysis takes into account the relevant interactions among the torsional stacks of levels in the gs, ν₁₂, and ν₅. These include the previously known (gs, ν₁₂) Coriolis-like and (gs, ν₅) Fermi-like interactions along with a higher order (ν₁₂, ν₅) Coriolis-like coupling introduced here. This last is responsible for the strong perturbation of the ν₅ series with K = 10, 11, and 12, and of the corresponding hot band series. A good fit to 9282 frequencies including 7942 new measurements was obtained both with the Free Rotor model in which the torsion is classified as a rotation, and with the High Barrier model in which the torsion is classified as a vibration. The Hamiltonian is discussed with emphasis on the new terms required for treating ν₁₂ + ν₆ − ν₆.     

Rovibrational spectroscopy of the Fermi-interacting ν4 = 1 and ν3 = ν6 = 1 levels of DCF3

The high-resolution infrared spectrum of deuterated fluoroform (DCF₃) was studied in the 700 and 1200 cm⁻¹ regions, with the aim of assigning and analyzing the ν₄ CF₃ asymmetric stretching vibration. The Fermi-type anharmonic coupling between the ν₄ = 1 and ν₃ = ν₆ = 1 rovibrational levels, already mentioned in an early work of Ruoff et al. [Spectrochimica Acta Part A 31A (1975) 1099-1100], was studied here for the first time under high resolution. Assignments in the ν₃ + ν₆/ν₄ band system were confirmed and extended by the identification of the ν₃ + ν₆ − ν₆ and ν₄-ν₆ bands in the 700 cm⁻¹ region, the latter being enhanced near the Fermi crossings of the studied levels. Data from both the hot and difference bands were included in the analysis. The close separation of the studied vibrational levels of about 14.8 cm⁻¹ produces a large variety of resonance crossings which involve levels with . Besides the Fermi () and Coriolis () resonances, they were accounted for by inclusion of additional higher-order ( and ) interaction terms between the vibrational states. The least-squares fit of more that 16,000 vibration-rotation transitions provides a quantitative reproduction of data in all bands.     

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.     

The high resolution infrared bands ν1, ν2, ν4 and ν2 + ν5 of FClO3

The high resolution infrared spectrum of mono-isotopic F³⁷Cl¹⁶O₃ has been studied in the regions of ν₁, ν₂, ν₄ and ν₂ + ν₅ bands, centered at 1060.20, 707.16, 1301.71 and 1292.15 cm⁻¹, respectively. The ν₁ and ν₂ parallel bands are unperturbed so their analysis was straightforward and 3355 and 2433 transitions were assigned, respectively. The band origins, the rotational and centrifugal molecular constants in the v₁ = 1 and v₂ = 1 states have been determined, with standard deviation of the fits σ = 0.00019 and 0.00018 cm⁻¹. The ν₄ fundamental is affected by an anharmonic resonance with the ν₂ + ν₅ combination band. The kl > 0 sublevels cross at kl ? 27 because of the opposite values of and . The anharmonic resonance constant  cm⁻¹ has been derived. The Δl = Δk = ±2 and Δl = 0, Δk = ±3 essential resonances have been found to be effective in ν₄, while in ν₂ + ν₅ only the Δl = Δk = ±2 one was active. A total of 5721 transitions have been assigned, 25% of them belonging to ν₂ + ν₅. The rovibrational parameters and the interaction constants of F³⁷Cl¹⁶O₃ have been obtained. The standard deviation of the fit is 0.0006 cm⁻¹, six times the estimated data precision. The equilibrium geometry of perchloryl fluoride has been determined from the A_e and B_e constants of F³⁵Cl¹⁶O₃ and F³⁷Cl¹⁶O₃. Using the A₀ and B₀ constants of all the symmetric species the r₀ geometry has also been derived.     

The ν7, ν8, and ν11 bands of propynal, C2HCHO, in the 650 cm region

The infrared spectrum of propynal, C₂HCHO, is studied at high resolution (0.003 cm⁻¹) in the range 570-640 cm⁻¹. The relatively intense ν₁₁ (CC-H out-of-plane bend, 693 cm⁻¹) and ν₇ (CC-H in-plane bend, 651 cm⁻¹) fundamental bands are linked by a strong a-type Coriolis interaction. The somewhat weaker ν₈ (CCO in-plane bend, 614 cm⁻¹) fundamental has a significant Fermi-type interaction with the “dark” background state 3ν₉ (∼618 cm⁻¹). About 1400 lines are assigned and analyzed in terms of a four-state fit in order to obtain accurate band origins, rotational and centrifugal distortion parameters, and Fermi and Coriolis interaction parameters. This represents the first systematic high-resolution infrared study of propynal.     

High-resolution infrared and microwave study of the ν20 and ν21 levels near 300 cm in 1,2,4-triazine

The gas phase far-IR spectrum of the ν₂₀ (A″, 367.88 cm⁻¹) and ν₂₁ (A″, 311.28 cm⁻¹) bands of 1,2,4-triazine, a five membered ring having the point group C_s, has been studied at a resolution ranging from 0.002 to 0.003 cm⁻¹. From the MW spectrum 58 transitions in the ν₂₀ level and 64 in the ν₂₁ level have been assigned. The ν₂₀ and ν₂₁ modes which are due to non-planar motions of the ring system are found to be nearly unperturbed. From a simultaneous analysis of IR and MW transitions band centers, rotational constants, and the quartic centrifugal distortion constants , and δ_K have been obtained using the Watson Hamiltonian, A-reduction, III^r-representation.     

High-resolution synchrotron infrared spectroscopy of thiophosgene: The ν2 and ν4 fundamental bands near 500 cm

Thiophosgene (Cl₂CS) is a favorite model system for studies of photophysics, vibrational dynamics, and intersystem interaction effects. But there are no previous rotationally-resolved infrared studies because the spectra are very congested due to hot bands and multiple isotopic species. This paper reports a detailed study of the ν₂ (∼504 cm⁻¹) and ν₄ (∼471 cm⁻¹) fundamental bands for the two most abundant isotopomers, ³⁵Cl₂CS and ³⁵Cl³⁷ClCS, based on spectra with observed line widths of ∼0.0008 cm⁻¹ obtained at the Canadian Light Source far-infrared beamline using synchrotron radiation and a Bruker IFS125 Fourier transform spectrometer.     

Infrared spectra of the polar and nonpolar N2O dimers in the 1280 cm region of the ν3 fundamental

The high-resolution infrared spectrum of the polar N₂O dimer has been observed in the region of the N₂O ν₃ fundamental (∼1280 cm⁻¹) using a tunable diode laser to probe a pulsed supersonic slit jet. About 120 rotational transitions were assigned in terms of an a/b hybrid band of a planar asymmetric top molecule with a slipped parallel structure. The vibrational origin was determined to be 1290.21 cm⁻¹, showing a blue shift of 5.31 cm⁻¹ with respect to the monomer band origin. In addition, the spectrum of the nonpolar isomer at 1279.71 cm⁻¹ has been remeasured and analyzed in improved detail. Small but widespread perturbations are noted in this band, which appear somewhat similar to larger effects observed previously in the ν₁ + ν₃ region for nonpolar (N₂O)₂.     

Frequency comb-referenced measurements of self- and nitrogen-broadening in the ν1 + ν3 band of acetylene

We report measurements of self- and nitrogen-pressure broadening of the P(11) line in the ν₁ + ν₃ combination band of acetylene at 195 739.649 5135(80) GHz by absorption of radiation emitted by an extended cavity diode laser referenced to a femtosecond frequency comb. Broadening, shift and narrowing parameters were determined at 296 K. For the most appropriate, hard collision, model in units of cm⁻¹/atm, we find 0.146317(27), 0.047271(104) and −0.0070819(22) for the acetylene self-broadening, narrowing and shift, and 0.081129(35), 0.022940(74) and −0.0088913(25) respectively, for the nitrogen-broadening parameters. The uncertainties are expressed as one standard deviation (in parenthesis) in units of the last digit reported. These parameters are 2-3 orders of magnitude more precise than those reported in previous measurements. Similar analyses of the experimental data using soft collision and simple Voigt lineshape models were made for comparison.     

The ν4 and ν2 + ν5 high resolution infrared bands of FClO3 and FClO3

The high resolution infrared spectra of monoisotopic F³⁵Cl¹⁸O₃ and F³⁷Cl¹⁸O₃ have been studied in the region of the ν₄ fundamentals, centered at 1278.3 and 1263.3 cm⁻¹, respectively. Large perturbations are observed in both bands due to a Fermi type anharmonic resonance with the ν₂ + ν₅ combination bands, centered at 1270.7 cm⁻¹ in F³⁵Cl¹⁸O₃ and 1257.3 cm⁻¹ in F³⁷Cl¹⁸O₃. In particular, they affect the kl > 0 levels of the v₄ = 1 and v₂ = v₅ = 1 states which cross at kl ? 18 in F³⁵Cl¹⁸O₃ and kl ? 3 in F³⁷Cl¹⁸O₃, due to the opposite values of and . The Δl = Δk = ±2 and Δl = 0, Δk = ±3 essential resonances are also effective in the excited states of the dyad in F³⁵Cl¹⁸O₃, while in F³⁷Cl¹⁸O₃ only the Δl = Δk = ±2 one is active. In the spectrum of F³⁵Cl¹⁸O₃ 3423 transitions have been assigned, 10% of them belonging to ν₂ + ν₅. The rovibrational parameters and the interaction constants between the v₄ = 1 and v₂ = v₅ = 1 levels have been obtained. The depertubed band origins of ν₄ and ν₂ + ν₅ are 1277.310567(165) and 1271.753733(195) cm⁻¹, respectively, and the anharmonic resonance constant is 2.804416(153) cm⁻¹. For F³⁷Cl¹⁸O₃, 3022 transitions have been assigned, 38% belonging to the ν₂ + ν₅ combination band. The depertubed band origins are 1260.856338(123) and 1259.872338(134) cm⁻¹, for ν₄and ν₂ + ν₅ and the constant is 2.9350669(405) cm⁻¹. The equilibrium geometry of perchloryl fluoride, r_e (ClO) = 139.7(3) pm, r_e (ClF) = 161.0(5) pm, and α_e (OClO) = 115.7(4) degree, has been determined using the A_e and B_e equilibrium constants of the four symmetric isotopologues of perchloryl fluoride, F^35/37Cl¹⁶O₃ and F^35/37Cl¹⁸O₃.     

High resolution Fourier transform infrared spectra and analysis of the ν14, ν15 and ν16 bands of azetidine

Rotationally resolved vibrational spectra of the three lowest frequency bands of the four-membered heterocycle azetidine (c-C₃H₆NH) have been collected with a resolution of 0.00096 cm⁻¹ using the far infrared beamline at the Canadian Light Source synchrotron. The modes observed correspond principally to motions best described as: β-CH₂ rock (ν₁₄) at 736.701310(7) cm⁻¹, ring deformation (ν₁₅) at 648.116041(8) cm⁻¹, and the ring puckering mode (ν₁₆) at 207.727053(9) cm⁻¹. A global fit of 14 276 rovibrational transitions from the three bands provided an accurate set of ground state spectroscopic constants as well as excited state parameters for each of the three vibrational modes. The ground state structure was determined to be that of the puckered conformer having the NH bond in an equatorial arrangement.     

New analysis of the ν5+ν9−ν9 hot band of HNO3

Nitric acid which is an important NO_x atmospheric reservoir molecule exhibits a strong absorption in the spectral region. Since this region, which corresponds to an atmospheric window, is one of the most commonly used for the retrieval of HNO₃ in the atmosphere it is essential to have the best possible corresponding spectral parameters. Updates of these spectral line parameters were recently performed in the last versions of the atmospheric databases. They concern the line positions and intensities not only of the two interfering cold bands ν₅ and 2ν₉ but also of the ν₅+ν₉−ν₉ hot band. This hot band exhibits indeed a sharp and strong Q branch at which is clearly observable in atmospheric spectra and is used for the retrievals. However, in spite of these recent updates, it proved that the spectral parameters of the hot band are not accurate enough to reproduce accurately the observed atmospheric HNO₃ absorption in ATMOS spectra. The present paper is dedicated to a more accurate analysis of this hot band using new laboratory high-resolution (0.002-) Fourier transform spectra. As a consequence, new and more precise line positions and line intensities (about 35% weaker than in HITRAN2K) were derived leading to a significant improvement in the simulation of atmospheric spectra.     

Simultaneous analysis of the 2ν2, 2ν5, and ν2 + ν5 vibration-rotation bands of CH3Br

Previous studies of the parallel bands 2ν₂ and $\text{2ν}{}_5{}^0$ of CH₃Br by the two first authors have been completed by the analysis of the weaker perpendicular band ν₂ + ν₅, centered near 2745 cm^?1. It is well known that the v₂ = 1 and v₅ = 1 states of methylbromide are linked by an x-y-type Coriolis interaction. Therefore, in the 2500–2900-cm^?1 range, the levels

$\text{(v}{}_2\text{=2), (v}{}_5\text{2, l}{}_5\text{=0), (v}{}_5\text{=2, l}{}_5\text{±2), (v}{}_5\text{=v}{}_2\text{=1, l=5±1)}$

are linked by a similar interaction. Least-squares and prediction programs have been written to treat this kind of problems and they have been satisfactorily applied to both isotopic species, CH₃⁷⁹Br and CH₃⁸¹Br. A localized resonance in the K = 0 subband of ν₂ + ν₅ has been shown to be due to the 3ν₃ + ν₆ band. No evidence for a strong Fermi resonance between ν₁ and $\text{2ν}{}_5{}^0$ has been found.     

First analysis of the ν5 band of DNO3 (deuterated nitric acid) in the 11 μm region

The infrared spectrum of DNO₃ (deuterated nitric acid) was recorded at high resolution (0.0027 cm⁻¹) in the 700-1400 cm⁻¹ region on a Bruker IFS 120 HR Fourier transform spectrometer. The analysis of the ν₅ band of DNO₃ centred at 887.657 cm^-1 which is mostly an A-type band, was performed making use of the ground state parameters achieved by Drouin et al. [Drouin BJ, Miller CE, Fry JL, Petkie DT, Helminger P, Medvedev IR. J Mol Spectrosc 2006;236:29-34]. The ν₅ fundamental band is strongly perturbed because of the existence of the ν₇+ν₉ dark combination band at 882.21  cm^-1. The 5¹ and 7¹9¹ energy levels of DNO₃ are coupled through A and B type Coriolis resonances, and as a consequence, numerous lines from the ν₇+ν₉ dark combination band could be identified also. In this way about 1070 and 75 energy levels of the 5¹ and 7¹9¹ vibrational states, respectively, were satisfactorily reproduced by the energy levels calculation which account for the observed resonances. A reasonable estimation of the absolute line intensities for the ν₅ band of DNO₃ was performed using the ν₅ transition operator from H¹⁴NO₃. The spectrum also features the ν₅+ν₆−ν₆, ν₅+ν₇−ν₇ and ν₅+ν₉−ν₉ hot bands located at 881.03, 882.61 and 884.45 cm⁻¹, respectively.     

High-resolution study of the ν1/ν5 and 2ν1/ν1+ν5 P-H stretching bands of PH2D

The P-H stretching bands ν₁/ν₅ and 2ν₁/ν₁+ν₅ were recorded using a Bruker 120 HR interferometer with a resolution of 0.0042 and 0.0088 cm⁻¹, respectively, and analyzed. From the fits 33 and 50, respectively, vibrational, rotational, centrifugal distortion, and resonance interaction parameters were obtained. These reproduce 668 and 497 rovibrational energies of the pairs of states ν₁/ν₅ and 2ν₁/ν₁+ν₅ with experimental accuracies, rms=0.00016 and , respectively. “Local mode” behavior of the PH₂ fragment is established and discussed in detail.     

FTIR spectra of the ν6 and ν8 bands of C formic acid molecule—Assignment of FIR-laser lines

Two interacting vibrational modes ν₆ and ν₈ of ¹³C species of formic acid have been studied with high resolution FTIR spectroscopy in the range 900-1300 cm⁻¹ with an instrumental resolution of 0.0018 cm⁻¹. More than 10 000 lines have been assigned and fitted with a RMS deviation of 0.00024 cm⁻¹. The band centers, as well as the rotational, quartic and sextic centrifugal distortion parameters and 6 interaction parameters have been determined. The obtained parameters have enabled the assignments of 24 FIR laser emissions of this molecule observed previously by Dangoisse and Glorieux [D. Dangoisse, P. Glorieux, J. Mol. Spectrosc. 92 (1982) 283-297], Luis et al. [G.M.R.S. Luis, E.M. Telles, A. Scalabrin, D. Pereira, IEEE J. Quantum. Electron. QE-34 (1998) 767-769], and Bertolini et al. [A. Bertolini, G. Carelli, C.A. Massa, A. Moretti, F. Strumia, Infrared Phys. Technol. 40 (1999) 33-36].