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 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 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.     

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.     

High-resolution infrared Fourier transform spectroscopy of SO in the X3Σ− and a1Δ electronic states

The v = 1 ← 0 vibration-rotation absorption bands of ³²S¹⁶O, ³⁴S¹⁶O, and ³²S¹⁸O in the ground electronic state, X³Σ⁻, and the v = 1 ← 0 vibration-rotation band of ³²S¹⁶O in the first excited electronic state, a¹Δ, were measured at 0.004 cm⁻¹ unapodized resolution with a high-resolution Fourier transform spectrometer coupled to a long path absorption cell. The v = 2 ← 0 vibration-rotation band of ³²S¹⁶O in the X³Σ⁻ state was also observed. Line positions for P- and R-branch transitions up to N = 44 for ³²S¹⁶O have been measured and analyzed yielding improved molecular parameters. The present measurements are compared with previous infrared and microwave measurements.     

Laser spectroscopy of perturbed states of BaO in the region above 32 000 cm−1

The excitation spectrum of BaO in the region above 32 000 cm⁻¹ was investigated with a frequency-doubled pulsed dye laser. We have observed fully developed rotational structures of the C¹Σ⁺-X¹Σ⁺ transition. The analysis of the vibrational states v′ = 0 through 7 leads to a large number of perturbations. This spectroscopic information in combination with the observation and rotational analysis of transitions to several new electronic states allows a systematic summary, which gives more than eight electronic states in the investigated region. Besides the known states B, C, D and c, we find four new bound states, designated by E, F, G, and H. For all states molecular constants are given. The discussion of possible molecular electron configurations leads to classifications of the molecular electronic states. Our results on the vibrational levels v′ = 0 to 3 are in reasonable agreement to the optical-optical double resonance work of R. A. Gottscho, P. S. Weiss, and R. W. Field [J. Mol. Spectrosc. 82, 283–309 (1980)], but show several new details.     

LED-based Fourier-transform spectroscopy of H2 18O in the range 15000–15700 cm−1

The spectrum of H₂ ¹⁸O in the range 15000–15700 cm^?1 has been recorded for the first time on a Fourier-transform spectrometer using a high-brightness light-emitting diode as a radiation source. The measurements have been conducted at room temperature with a resolution of 0.05 cm^?1. A threshold sensitivity in absorption of 2 × 10^?7 cm^?1 has been achieved due to both the use of a light-emitting diode and optimization of the multipass cell with a base length of 60 cm, which ensured a 19.2-m length of the absorbing layer. A high signal-to-noise ratio (S/N = 2000–10000) made it possible to record about 670 water-vapor lines with intensities of 1.0 × 10^?26–2.2 × 10^–24 cm/mol at 296 K. The energies of 265 vibrational-rotational levels of the H₂ ¹⁸O molecule are determined and attributed to seven vibrational states, namely, (033), (113), (212), (231), (311), (330), and (410).     

High-resolution FTIR spectra of CH2 = CClF in the 930-1050 cm−1 region

The gas-phase infrared spectra of natural CH₂ = CClF have been measured in the v ₆ and 2v ₁₂ band regions (930–1050 cm^?1) by high-resolution Fourier transform spectroscopy at room temperature. 1-Chloro-1-fluoroethylene is a planar asymmetric rotor (κ = ?0.54) belonging to the symmetry point group C_s and the vibrations investigated of symmetry species A′ give rise to a/b-hybrid bands with contributions of comparable intensity from both the components.

The rovibrational analysis of the fine structure led to the identification of 1894 (J ? 73, K_a ? 20) and 718 (J ? 53, K_a ? 8) transitions for the v ₆ and 2v ₁₂ bands of the ³⁵Cl isotopic species, respectively. Using the Watson's A-reduction Hamiltonian in the I^r representation a set of accurate spectroscopic parameters for both the excited states u ₆ = 1 and u12 = 2 of ³⁵Cl has been obtained for the first time. Transitions of ³⁷Cl isotopomer could also be assigned in the Q branch region of the 2v ₁₂ overtone; the determined band origin shift of 0.782 cm^?1 towards the lower wavenumbers led to describing the v ₁₂ fundamental as a vibration mainly involving the CFCl bending motion.     

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.     

Infrared spectroscopy of 17O- and 18O-enriched carbon dioxide in the 1700–8300 cm−1 wavenumber region

The assignment of the high resolution Fourier transform spectra of carbon dioxide enriched in ¹⁷O and ¹⁸O which were recorded in LADIR (Paris, France) with the Bruker IFS 125-HR between 1800 and 9000 cm^?1 and in USTC (Hefei, China) with the Bruker IFS 120-HR between 1700 and 9000 cm^?1 was performed. In total 239 bands of 12 isotopologues: ¹⁶O¹²C¹⁶O, ¹⁶O¹²C¹⁸O, ¹⁶O¹³C¹⁶O, ¹⁶O¹³C¹⁸O, ¹⁸O¹²C¹⁸O, ¹⁸O¹³C¹⁸O, ¹⁶O¹²C¹⁷O, ¹⁷O¹²C¹⁷O, ¹⁷O¹²C¹⁸O, ¹⁶O¹³C¹⁷O, ¹⁷O¹³C¹⁷O and ¹⁷O¹³C¹⁸O were observed. Among them, 99 bands were observed for the first time. The majority of new observed bands belong to ¹⁷OCO isotopologues. The positions of 23,003 lines were determined with the experimental uncertainty on the level of 0.001 cm^?1. The spectroscopic constants were fitted to the observed line positions for all observed bands.     

High-resolution spectroscopy of the a4Σ−3/2 − X12Π3/2 system of gold monosulphide in the near infrared

ABSTRACT

We have recorded the a⁴Σ^? _3/2 ? X₁ ²Π_3/2 (0,0), (1,0), and (2,0) bands of gaseous gold monosulphide (AuS) at sub-Doppler resolution in the near-infrared region. The molecules were made in a hollow cathode discharge source by the reaction of sputtered gold with carbonyl sulphide. The high resolution of the laser excitation spectrum enabled the determination of molecular constants describing the rotational and ¹⁹⁷Au hyperfine structure in both states, as well as the spin–rotation interaction in the a⁴Σ^? _3/2 state. The natures of the two electronic states are discussed in the context of the observed hyperfine structure.     

High resolution infrared and Raman spectroscopy of ν 2 and associated combination and hot bands of 13C12CD2

Infrared and Raman spectra of dideuterated acetylene containing one ¹³C atom, ¹³C¹²CD₂, have been recorded and analysed to obtain detailed information on the fundamental ν ₂ band and associated combination and hot bands. Infrared spectra were recorded at 4?×?10^?3?cm^?1 resolution in the region 1150?2900^?cm^?1, which contains combination and hot bands from the ground and the bending v ₄?=?1 and v ₅?=?1 states. The Q-branches of the ν ₂ fundamental and associated hot bands (ν ₂?+?ν ₄???ν ₄, ν ₂?+?ν ₅???ν ₅, ν ₂?+?2ν ₄???2ν ₄, ν ₂?+?2ν ₅???2ν ₅ and ν ₂?+?ν ₄?+?ν ₅???(ν ₄?+?ν ₅)) were recorded using inverse Raman spectroscopy, with an instrumental resolution of about 3?×?10^?3?cm^?1. In addition, the observation of the 2ν ₂???ν ₂ Raman band was carried out populating the v ₂?=?1 state by stimulated Raman pumping. In total, 11 Raman and 9 infrared bands were analysed, involving all the l-vibrational components of the excited stretching?bending manifolds up to v _t ?=?v ₄?+?v ₅?=?2.

A simultaneous analysis of all infrared and Raman assigned transitions has been performed on the basis of a theoretical model which takes into account the rotation and vibration l-type resonances within each vibrational manifold and the Darling?Dennison anharmonic resonance between the ν ₂?+?2ν ₄ and ν ₂?+?2ν ₅ states. The parameters obtained reproduce the assigned transition wavenumbers with a standard deviation of the same order of magnitude as the experimental uncertainty.     

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.     

High-resolution spectroscopy of 16 bands of OCS in the region 1975–2140 cm−1 for diode laser calibration

The spectrum of OCS with natural isotopic abundances has been measured in the 1975- to 2140-cm^?1 region with near-Doppler-limited resolution using a Fourier transform spectrometer. Sixteen bands have been analyzed, including the following five bands for the first time at high resolution:

     

18.

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

D. HURTMANS  S. KASSI  C. DEPIESSE  M. HERMAN 《Molecular physics》2013,111(22):3507-3511

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.     

19.

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

O.M. Lyulin  A.V. Nikitin  V.I. Perevalov  Isamu Morino  Tatsuya Yokota  Ryoichi Kumazawa  Takeshi Watanabe 《Journal of Quantitative Spectroscopy & Radiative Transfer》2009,110(9-10):654-668

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.     

20.

Fourier transform spectroscopy of methanol: Taylor coefficients for the region between 8 and 80 cm−1     

《Infrared physics》1985,25(1-2):251-253

In our systematic investigation of the FTS of CH₃OH we have assigned about 3000 lines connecting levels of the vibrational ground state with frequencies between 8 and 80 cm⁻¹. Here we present the parameters for Taylor expansions of the energy levels in J(J + 1) which allow us to reconstruct the spectral lines with a precision usually of the order of 10⁻⁴cm⁻¹.     

16O13C32S	1000-0000	2009.228 cm?1
16O13C32S	1110-0110	2002.427 cm?1
18O12C32S	1000-0000	2026.147 cm?1
16O12C32S	0400-0000	2104.828 cm?1
16O12C32S	0510-0110	2115.169 cm?1

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.     

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.     

Fourier transform spectroscopy of methanol: Taylor coefficients for the region between 8 and 80 cm−1

In our systematic investigation of the FTS of CH₃OH we have assigned about 3000 lines connecting levels of the vibrational ground state with frequencies between 8 and 80 cm⁻¹. Here we present the parameters for Taylor expansions of the energy levels in J(J + 1) which allow us to reconstruct the spectral lines with a precision usually of the order of 10⁻⁴cm⁻¹.