The infrared spectrum of isothiazole in the range 600–1500 cm−1, including a high-resolution study of the v 11(A′) band at 818 cm−1 and the v 16(A″) band at 727 cm−1, together with ab initio studies of the full spectrum

Abstract

The gas-phase high-resolution infrared spectrum of isothiazole in the range 600–1500 cm^?1 has been recorded, and revised band centres obtained for a number of vibrations. An analysis of the v ₁₁(A′) band at 818 cm^?1 and the v ₁₆(A″) band at 727 cm^?1 has been performed, using the Watson Hamiltonian, A-reduction, III^r representation. These were combined with previous microwave spectral data to provide combined analyses for rotational constants and quartic centrifugal distortion constants Δ _J , Δ _JK , Δ _K , δ _j and δ _K . These extend the knowledge derived from previous microwave and IR spectral studies. The equilibrium structures and the derived harmonic frequencies were calculated by ab initio methods, using a variety of basis sets with MP2, MP4 and CCSD(T) methods, and a comparison of these with experimental data is discussed. At a pragmatic level, the closest correlation of the rotational constants with experiment is not obtained with the most sophisticated methodology. Similarly, the vibration frequencies and intensities also vary strongly with the procedure. In particular, we found that the cc-pVTZ+MP2 results probably provide the best numerical comparison with experimental IR data for this molecule.     

The high-resolution infrared spectrum of HBF2: The 401 band near 926 cm−1

The type-C out-of-plane bending fundamental ν₄ (near 926 cm⁻¹) in the infrared spectrum of gaseous difluoroborane, HBF₂, has been recorded at high resolution. Rotational and centrifugal distortion constants have been obtained for the two isotopic species H¹⁰BF₂ and H¹¹BF₂ in both the ground and 4¹ levels. A small rotational perturbation in the 4¹ level of H¹¹BF₂ has allowed an estimate of the position of the ν₆ fundamental, which so far has not been observed directly.     

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.     

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.     

Infrared spectrum of the Ar-CO complex: observation of the v co = 2 ← 0 band at 4260 cm −1

The spectrum of the weakly-bound van der Waals complex Ar-CO has been observed for the first time in the region of the CO vibrational overtone, using a long-path (180 m) low-temperature (64 K) absorption cell and a Fourier transform infrared spectrometer. The appearance of the spectrum was very similar to that studied previously in the v _co = 1 ← 0 region. However, it was very much weaker, so a detailed analysis was only possible for the relatively uncongested K = 1 ← 0 and 0 ← 1 subbands. The parameters determined here for these sub-bands should help to constrain the C-O bond length dependence of the Ar-CO intermolecular potential in future theoretical models.     

The high-resolution spectrum of the ν1 (A1) band of 12CD3F

The spectrum of the ν₁ (A₁) band of ¹²CD₃F has been recorded with a resolution of 0.010 cm⁻¹ and deconvolved to 0.005 cm⁻¹. Over 1050 transitions have been assigned with K ≤ 16 and J ≤ 42. The spectrum is highly perturbed, exhibiting avoided crossings in most of the observed sub-bands. The origin of most of the local and global resonances has been determined and the coupling constants estimated. Due to the complexity of the spectrum resulting from the 24 potential interacting states in the region, the assigned frequencies were fitted in a restricted manner (K ≤ 3, J ≤ 15), to obtain the following effective constants for the band: ν₀ = 2090.8118(20) cm⁻¹, α^A = 1.19743 × 10⁻² cm⁻¹, and α^B = −1.8489 × 10⁻³ cm⁻¹. From an unrestricted least-squares analysis, fixing the above parameters the β's (D_v^x = D₀^x − β_v^x) were calculated to be β^J = 1.7776 × 10⁻⁷ cm⁻¹, β^JK = 8.3406 × 10⁻⁷ cm⁻¹, and β^K = −6.3829 × 10⁻⁷ cm⁻¹. These constants serve as good starting parameters for the global analysis necessary to fully analyze the 5-μm region of the ¹²CD₃F spectrum.     

Fourier transform infrared spectrum of carbon disulphide in the 4ν2 + ν3 band region near 3100 cm−1

Fourier transform spectra have been recorded for carbon disulphide CS₂ in the region of the 4ν₂ + ν₃ band near 3100 cm^?1. The data analysis has determined new molecular constants. Bands were also observed for the isotopomer ¹²C³²S³⁴S.     

Estimation of the energy spectrum of cosmic ray electrons at the atmospheric depth (3.8–7.4)g.cm−2

Analytical calculations have been done to estimate the energy spectra of the secondary electrons originated from the decay of charged and neutral pions initiated on the upper atmosphere from the primary nucleon–air interactions in the energy range (4–100) GeV. The calculations are valid up to an atmospheric depth of about (3.8–7.4) g.cm^–2. The derived results are compared with the observed electron fluxes available from the balloon flight experiments of MASS2, HEAT, magnetic spectrometer system of Golden et al., instrument using scintillating fibers of Nishimura et al., and BETS.     

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.     

Investigation of new band parameters with temperature dependence for self-broadened methane gas in the range 9000 to 14,000 cm−1 (0.71 to 1.1 μm)

This paper describes new measurements and modelling of the absorption of methane gas, one of the most important gases observed in the atmospheres of the outer planets and Titan, between 9000 and 14,000 cm^?1 (0.7 to 1.1 μm) and compares them with current best available spectral models.A series of methane spectra were measured at the UK's Natural Environment Research Council (NERC) Molecular Spectroscopy Facility (based at the Rutherford Appleton Laboratory, Oxfordshire, UK) using a Brüker 125HR Fourier transform spectrometer. To approximate the conditions found in outer planet atmospheres, the spectra were measured over a wide range of pressures (5 bar to 38 mbar) and temperatures (290–100 K) with path lengths of 19.3, 17.6, 16.0 and 14.4 m. The spectra were recorded at a moderate resolution of 0.12 cm^?1 and then averaged to 10 cm^?1 resolution prior to fitting a series of increasingly complex band-models including temperature dependence. Using the most complex model, a Goody line distribution with a Voigt line shape and two lower energy state levels, the typical rms residual error in the fit is between 0.01 and 0.02 in the wings of the main absorption bands.The new spectral parameters were then compared with the measured spectra and spectra calculated using existing data and shown to be able to accurately reproduce the measured absorption. The improvement in the temperature dependence included in the model is demonstrated by comparison with existing cold methane spectral data for a typical Jovian path.     

The absorption spectrum of methane at 80 and 294 K in the icosad (6717–7589 cm−1): Improved empirical line lists,isotopologue identification and temperature dependence

Using a cryogenic cell and a series of Distributed Feed Back (DFB) diode lasers, new high resolution spectra of methane have been recorded at 80 K and room temperature by differential absorption spectroscopy (DAS) between 6717 and 7589 cm^?1 (1.49–1.32 μm). The investigated spectral region corresponds to the very congested icosad, which is not tractable by theory. Empirical lists of 19,940 and 24,001 lines were constructed from the 80 K and room temperature spectrum, respectively. The room temperature list adds about 8500 features to the empirical list of 15,375 lines at 296 K adopted in the HITRAN database from the original work of L. Brown (Brown, L. Empirical line parameters of methane from 1.1 to 2.1 μm. JQSRT 2005;96:251–70). A number of relatively strong CH₄ lines located near strong water lines were found missing in the HITRAN line list. The improved sensitivity allowed adding more than 7000 lines to our previous list of about 12,000 transitions at 80 K (Campargue A, Wang L, Kassi S, Ma?át M, Votava O. Temperature dependence of the absorption spectrum of CH₄ by high resolution spectroscopy at 81 K: (II) The Icosad region (1.49–1.30 μm). JQSRT 2010;111:1141–51). In order to facilitate identification of the transitions of the different methane isotopologues present in “natural” isotopic abundance, spectra of highly enriched CH₃D and ¹³CH₄ samples were recorded with the same experimental setup, both at room temperature and at 80 K.From the variation of the line strengths between 80 K and 294 K, the low energy values of about 12,000 transitions were determined. They allow accounting for the temperature dependence of 84 and 93% of the methane absorbance in the region, at room temperature and 80 K, respectively. As a result, we provide as supplementary material two complete line lists at 80 K and 294 K, including CH₃D and ¹³CH₄ identification and lower state energy values.     

The high-resolution infrared spectrum of thiophene between 600 and 1200 cm: A spectroscopic and theoretical study of the fundamental bands ν6, ν7, ν13, and the c-Coriolis interacting dyad ν5, ν19

The Fourier transform infrared spectrum of gaseous thiophene, C₄H₄S, has been recorded in the 600-1200 cm⁻¹ spectral region with a resolution of ca. 0.0030 cm⁻¹. Five fundamental bands ν₁₃ (B₁, 712.1 cm⁻¹), ν₇ (A₁; 840.0 cm⁻¹), ν₆ (A₁; 1036.4 cm⁻¹), ν₅ (A₁; 1081.5 cm⁻¹) and ν₁₉ (B₂; 1084.0 cm⁻¹) have been analysed by the standard Watson model (A-reduction). Ground state rotational and quartic centrifugal distortion constants have been obtained from a simultaneous fit of ground state combination differences from four of these bands and previous microwave transitions. Upper state spectroscopic constants have been obtained for all five bands from single band fits using the Watson model. A strong c-Coriolis resonance perturbs the close lying ν₅ and ν₁₉ bands. We have analysed this dyad system by a model including first and second order Coriolis resonance using the theoretically predicted Coriolis coupling constant . From this analysis we locate the previously unobserved ν₁₉ band at 1083.969 cm⁻¹. The rotational constants, ground state quartic centrifugal distortion constants, anharmonic frequencies, and vibration-rotational constants (α-constants) predicted by quantum chemical calculations using a cc-pVTZ basis with B3LYP methodology, are compared with the present experimental data, where there is generally good agreement. A complete set of anharmonic frequencies and α-constants for all fundamental levels of the molecule is given.