The high-resolution infrared spectrum of ethylene in the 1800–2350 cm−1 spectral region

Fourier transform spectra of ethylene (C₂H₄) have been recorded in the 1800–2350?cm^?1 (4.3–5.6?µm) spectral region using a Bruker IFS125HR spectrometer at a resolution of 0.004?cm^?1 leading to the observation of six vibrational bands, ν ₇?+?ν ₈, ν ₄?+?ν ₈, ν ₆?+?ν ₁₀, ν ₆?+?ν ₇, ν ₄?+?ν ₆ and ν ₃?+?ν ₁₀. The corresponding upper state ro-vibrational levels were fit using a Hamiltonian matrix accounting for numerous interactions. A satisfactory fit could be obtained using a polyad of nine interacting states {8¹10¹,?7¹8¹,?4¹8¹,?8¹12¹,?6¹10¹,?6¹7¹,?4¹6¹,?3¹10¹,?3¹7¹} of which three (8¹10¹, 8¹12¹ and 3¹7¹) are unobserved dark states. As a result a much more accurate and extended set of Hamiltonian constants were obtained than previously derived. The following band centers were determined: ν ₀(ν ₇?+?ν ₈)?=?1888.9783(20)?cm^?1, ν ₀(ν ₄?+?ν ₈)?=?1958.2850(20)?cm^?1, ν ₀(ν ₆?+?ν ₁₀)?=?2047.7589(20)?cm^?1, ν ₀(ν ₆?+?ν ₇)?=?2178.011(60)?cm^?1, ν ₀(ν ₄?+?ν ₆)?=?2252.8026(24)?cm^?1 and ν ₀(ν ₃?+?ν ₁₀)?=?2171.2397(20)?cm^?1. Finally, a synthetic spectrum that could be useful for ethylene detection in planetary atmospheres was generated.     

The absorption spectrum of 12C2H2 IV. The regions 7600–9200 cm−1 and 10600–11500 cm−1

The absorption spectrum of ¹²C₂H₂ has been recorded by intracavity laser absorption spectroscopy (ICLAS) in the 10600–11 500 cm^?1 spectral region, where no absorption bands were previously reported. Fifteen bands starting from the vibrational ground state are observed and rotationally analysed. All corresponding excited vibrational levels were assigned using the polyad model, the so-called cluster model (El Idrissi, M.I., Liévin, J., Campargue, A., and Herman, M., 1999, J. chem. Phys., 110, 2074) which allows vibrational energies, rotational B_v constants and, to some respect, relative band intensities to be predicted. Additional data and constants are also provided in the range 7600–9200cm^?1, whenever improving the literature results, from spectra recorded previously at ULB using Fourier transform spectroscopy. The assignment procedure in the range recorded by ICLAS is detailed, leading to a deeper understanding of vibration-rotation and intensity features of the absorption bands within the frame of the cluster model.     

The infrared spectrum of 12C2HD: the stretching–bending combination bands in the 1800–4700 cm−1 region

The infrared spectrum of ¹²C₂HD has been observed between 1800 and 4700?cm^?1 by Fourier transform spectroscopy. The ν₁, ν₂ and ν₃ absorption bands and the associated hot and combination bands involving the bending modes up to υ_t?=?υ₄?+?υ₅?=?2 have been investigated. Altogether, 60 vibrational bands were analysed, leading to the spectroscopic characterization of 31 vibrationally excited states. Several perturbations have been observed, but the transitions involving the perturbing states have not been detected. As a consequence, an appropriate treatment of the vibrational or ro-vibrational interactions has not been possible. A tentative assignment of the perturbing states has been proposed. Eventually, global fits for each fundamental vibration and its associated cold and hot bands have been performed.     

The absorption spectrum of 12C2H2 between 12800 and 18500cm−1 II. Rotational analysis

The rotational structure of the vibrational bands of ¹²C₂H₂ is investigated in three spectral energy regions not previously systematically explored at high resolution, 12800–13500 cm^?1, 14000–15200 cm^?1 and 16500–18360 cm^?1, on the basis of new spectral data recorded by intracavity laser absorption spectroscopy. The rotational analysis of 17 new absorption bands arising from the ground state is reported (11 Σ_u ⁺ ? Σ_g ⁺ bands and 6Π_u ? Σ_g ⁺ bands). Four bands in the range studied show strong perturbations affecting both the line positions and intensities. Their detailed analysis is performed in order to determine the nature of the coupling schemes, the vibrational species and the rotational constants of the perturber states. Altogether, the vibration-rotation parameters of 21 newly observed vibrational states are derived.     

Assignment of a perturbation in the FT-ICLAS spectrum of 12C2H2 around 12 709.5 cm−1

The vibrational state perturbing the J = 17 and 18 rotational states of the zero-order v ₁ + 3v ₃ state of ¹²C₂H₂ is assigned to the state with vibrational energy predicted at G _ν = 12 685.1 cm^?1 using the cluster model (El Idrissi, M. I., Liévin, J., Campargue, A. and Herman, M., 1999, J. chem. Phys., 110, 2074). The assignment is discussed also in terms of the very special pressure shift behaviour demonstrated previously for absorption lines reaching these levels (Herregodts, F., Hepp, M., Hurtmans, D., Vander Auwera, J. and Herman, M., 1999, J. chem. Phys., 111, 7961). The experimental information arising from a set-up newly running at ULB, called FT-ICLAS brings decisive information in the assignment process. This set-up is described briefly.     

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.     

High-resolution infrared spectroscopy of H12C13CD and H13C12CD in the 470–5200 cm−1 spectral region

The fundamental ro-vibrational bands and the 2ν₄?←?GS, 2ν₅?←?GS, 2ν₃?←?GS, ν₄?+?ν₅?←?GS, ν₃?+?ν₄?←?GS, ν₃?+?ν₄?←?ν?₄, ν₃?+?ν₅?←?ν₅, overtone, combination and hot bands of the two rare isotopologues of acetylene H¹²C¹³CD and H¹³C¹²CD have been detected by Fourier transform infrared spectroscopy (FTIR). The analysis of the data has provided very accurate rotational and vibrational parameters for the ground and for the vibrationally excited states.     

The pentad of 12CD4: Line parameter analysis of the IR spectrum in the range 1775–2350 cm−1

In a previous paper (J.-E. Lolck, G. Poussigue, E. Pascaud, and G. Guelachvili, J. Mol. Spectrosc. 111, 235–274 (1985)), we presented the first comprehensive assignment and wavenumber analysis of high-resolution (nearly Doppler limited) rotation-vibrational spectra of the interacting upper states of the ν₁, ν₃, 2ν₂, ν₂ + ν₄, and 2ν₄ bands of the ¹²CD₄ pentad. The present paper continues this work by describing the determination and quality estimation of experimental infrared line strengths from the Fourier transform spectra. These line strengths are interpreted in terms of a theoretical model which contains, as parameters, the dipole moment derivatives and the main Hermann-Wallis coefficients of the infrared-allowed bands: ν₃(F₂), ν₂ + ν₄(F₂), and 2ν₄(F₂). This model also explains the appearance of infrared transitions to upper states, forbidden in infrared in an isolated state approach, through the mixing of states caused by the intervibrational interactions. The intensity analysis leads to the determination of all six parameters in the model and to a reproduction of the experimental intensities with a precision comparable to the experimental accuracy of 10 to 15%.     

The infrared spectrum of 13C2H2 in the 60–2600 cm−1 region: bending states up to v 4 + v 5 = 4

The vibration–rotation spectra of ¹³C substituted acetylene, ¹³C₂H₂, have been recorded in the region between 60 and 2600?cm^?1 at an effective resolution ranging from 0.001 to 0.006?cm^?1. Three different instruments were used to collect the experimental data in the extended spectral interval investigated. In total 9529 rotation vibration transitions have been assigned to 101 bands involving the bending states up to v _tot?=?v ₄?+?v ₅?=?4, allowing the characterization of the ground state and of 33 vibrationally excited states. All the bands involving states up to v _tot?=?3 have been analyzed simultaneously by adopting a model Hamiltonian which takes into account the vibration and rotation l-type resonances. The derived spectroscopic parameters reproduce the transition wavenumbers with a RMS value of the order of the experimental uncertainty. Using the same model, larger discrepancies between observed and calculated values have been obtained for transitions involving states with v _tot?=?4. These could be satisfactorily reproduced only by adopting a set of effective constants for each vibrational manifold, in addition to the previously determined parameters, which were constrained in the analysis.     

The FT absorption spectrum of 13CH12CH: rotational analysis of the vibrational states from 3800 to 6750 cm−1

Thirty four cold bands and 37 hot bands are reported from the high resolution FT absorption spectrum of ¹³CH¹²CH, all leading to vibrational states located between 3800 and 6750?cm^?1. Each band has been vibrationally assigned and rotationally analysed. The band centres and rotational constants are listed.     

Water-vapor continuum absorption in the 800–1250 cm−1 spectral region at temperatures from 311 to 363 K

About 200 pure water-vapor spectra covering the region from 800 to 3500 cm^?1 were recorded with resolution of 0.1 cm^?1 at temperatures 311, 318, 325, 339, 352, and 363 K using a 2 m base White cell coupled to the BOMEM DA3.002 FTIR spectrometer. The water-vapor pressure varied from 28 to 151 mbar (21–113 Torr). Under these conditions, the continuum absorbance is quite measurable with the available path lengths up to 116 m. A program was developed for spectral processing that calculates, fits, and removes ro-vibrational structure from the spectrum. The spectra obtained were used to retrieve averaged and smoothed binary absorption coefficients over the region from 800 to 1250 cm^?1. Our continuum data extrapolated to room temperature are in reasonable agreement with the MT_CKD continuum model. But at higher temperatures the MT_CKD model provides very low values, which are up to 50% less than those experimentally measured.     

Laser infrared spectroscopy of vinyl fluoride in the 1280–1400 cm−1 region

The infrared spectra of CH₂=CHF have been investigated in the ν₅ and ν₆ band regions between 1280 and 1400?cm^?1, at a resolution of about 0.002?cm^?1, using a tunable diode laser spectrometer. These vibrations of symmetry species A′ give rise to a/b-hybrid bands with different contributions from both the components. Spectral analysis resulted in the identification of 1565 (J≤46, K _a ≤11) and 1651 (J≤48, K _a ≤15) transitions of the ν₅ and ν₆ fundamentals, respectively. Both bands are perturbed by the nearby states ν₈?+?ν₉ and ν₉?+?ν₁₁ through different Coriolis resonances and an anharmonic interaction. Using Watson's A-reduction Hamiltonian in the I^r representation and perturbation operators almost all the transitions have been fitted simultaneously to a model including six resonances within the tetrad ν₅/ν₆/ν₈?+?ν₉/ν₉?+?ν₁₁. A set of spectroscopic constants for the ν₅ and ν₆ bands, as well as parameters for the dark states ν₈?+?ν₉ and ν₉?+?ν₁₁ and coupling constants, have been determined. From spectral simulations the dipole moment ratio |Δμ _a /Δμ _b | was estimated to be 0.6?±?0.1 and 2.0±0.3 for the ν₅ and ν₆ bands, respectively.     

The determination of complex refractive index spectra of liquids in the far-infrared spectral region 5–500cm−1, with dispersive Fourier transform spectrometry

The complex refractive index spectrum of transparent as well as very absorbing liquids is determined in the far-i.r. spectral region 5–500cm⁻¹ from dispersive interferograms obtained with a variable thickness, variable temperature cell containing the liquid specimen confined between a displaceable mirror and a plane-parallel window. The complex refractive index spectrum of the window material (e.g. hyperpure silicon, crystal quartz) is determined with the same experimental setup from an empty-cell interferogram.     

The infrared spectrum of gaseous cis-d2-ethylene below 1400 cm−1

Three infrared active fundamental bands of cis-d₂-ethylene have been studied at a resolution of ca. 0.030 cm⁻¹: the type-c band ν₇ and the two type-a bands ν₆ and ν₁₂. From a simultaneous analysis of infrared ground state combination differences due to ν₇ together with microwave measurements, a set of ground state rotational and centrifugal distortion constants has been obtained. For all three bands upper state spectroscopic constants are determined, and perturbations are identified. The K′_a = 4 level in ν₇ is perturbed locally by a higher order c-Coriolis resonance with ν₈. ν₆ is globally perturbed by first-order a-Coriolis resonances with ν₄ and ν₈. For ν₁₂ a higher order c-type Coriolis resonance with 2ν₁₀ is of importance for several K_a levels, and the constants for ν₁₂ have been obtained taking this interaction into account. In addition, a Coriolis resonance parameter and some constants for 2ν₁₀ have been determined.     

Measurements of N2- and O2-broadening and shifting parameters of methane spectral lines in the 5550–6236 cm−1 region

The absorption spectra of mixtures of methane (CH₄) with N₂ and O₂ at different partial pressures of both CH₄ and buffer gases for three temperatures 240, 267, and 296 K have been recorded using the Bruker IFS 125 HR FTIR spectrometer in the 5550–6236 cm^?1 region. The multispectrum fitting procedure has been applied to these spectra to recover the spectral line parameters. The main goal of this procedure was the determination of the N₂- and O₂-broadening and shifting coefficients and the exponents of their temperature dependences. These parameters have been derived for 452 assigned lines with good values of the signal to noise ratio. The rotational dependence of the mean values of these parameters is discussed. The temperature dependence exponents were observed for both N₂ and O₂ buffer gases.     

The Raman spectrum of C2D4 near 1000 cm−1: The Coriolis coupled ν3 and ν6 bands

The Raman spectrum of deuterated ethylene C₂D₄ has been investigated in the 1000-cm⁻¹ regions. The close-lying (16 cm⁻¹ apart) ν₃ and ν₆ bands are perturbed by a Coriolis interaction around the c axis with |ζ₃₆^c| = 0.39. This interaction distorts both the anisotropy and the trace spectra, which are presented as recorded in Aarhus and Madrid, showing also computer simulation of the contours. A least-squares refinement of around 300 transitions allows the determination of the ν₃ and ν₆ band origins and rotational constants.     

The high-resolution infrared spectrum of HBF2: The 201 band near 1164 cm−1

The type-B totally symmetric stretching fundamental ν₂ (near 1164 cm⁻¹) of difluoroborane has been recorded. Rotational and centrifugal distortion constants have been evaluated for the two isotopic species H¹⁰BF₂ and H¹¹BF₂, in both the ground and 2¹ levels. The spectrum has been found to be regular, with no perturbations and no new information on the position of the missing fundamental ν₆.