First far-infrared high-resolution analysis of the ν2 and ν4 bands of phosgene 35Cl2CO and 35Cl37ClCO

ABSTRACT

A Fourier transform spectrum of phosgene (Cl₂CO) has been recorded in the 17.3-μm spectral region at a temperature of 180 K and at a resolution of 0.00102 cm^?1 using a Bruker IFS125HR spectrometer coupled to synchrotron radiation, leading to the observation of the ν₂ and ν₄ vibrational bands of the two isotopologues ³⁵Cl₂CO and ³⁵Cl³⁷ClCO. The corresponding upper-state ro-vibrational levels were fit using a Hamiltonian model accounting for the A-type Coriolis interaction linking the rotational levels of the 2¹ and 4¹ vibrational states. In this way, it was possible to reproduce the upper-state ro-vibrational levels to within the experimental uncertainty, i.e. ～0.30 × 10^?3 cm^?1. Very accurate rotational and centrifugal distortion and interaction constants were derived from the fit, together with the following band centres: ν₀(ν_2, ³⁵Cl₂CO) = 572.526299(30) cm^?1, ν₀(ν_4, ³⁵Cl₂CO) = 582.089026(30) cm^?1, ν₀(ν_2, ³⁵Cl³⁷ClCO) = 568.951791(35) cm^?1 and ν₀(ν₄, ³⁵Cl³⁷ClCO) = 581.758279(35) cm^?1.     

The high-resolution spectrum of the ν1 + ν2 band of NO2: A spin-induced perturbation in the ground state

The spectrum of the ν₁ + ν₂ band of NO₂ has been studied with a resolution of 0.025 cm⁻¹. Spin-rotation constants and rotational constants are reported. An interesting perturbation has been found in the ground state of the molecule which occurs when the K_a = 0 and K_a = 2 levels become accidentally nearly degenerate around N = 42. An explanation of this interaction is presented.     

High-resolution analysis of the ν1 and ν5 bands of phosgene 35Cl2CO and 35Cl37ClCO

Fourier transform spectra of phosgene (Cl₂CO) have been recorded in the 11.75 and 5.47 μm spectral regions using a Bruker IFS125HR spectrometer at resolutions of 0.00102 and 0.0015 cm^?1, respectively, leading to the observation of the ν₅ and ν₁ vibrational bands of the two isotopologues ³⁵Cl₂CO and ³⁵Cl³⁷ClCO. The corresponding upper state ro-vibrational levels were fit using Watson-type Hamiltonians and/or a Hamiltonian matrix accounting for resonance effects when necessary. In this way, it was possible to reproduce the upper state ro-vibrational levels to within the experimental accuracy, i.e. ～0.17 × 10^?3 cm^?1. Very accurate rotational and centrifugal distortion constants were derived from the fit together with the following band centres: ν₀(ν_5, ³⁵Cl₂CO) = 851.012737(20) cm^?1, ν₀(ν_5, ³⁵Cl³⁷ClCO) = 849.995451(90) cm^?1, ν₀(ν_{2 +} ν_3, ³⁵Cl³⁷ClCO) = 864.42370(50) cm^?1, ν₀(ν_1, ³⁵Cl₂CO) = 1828.202514(40) cm^?1 and ν₀(ν_1, ³⁵Cl³⁷ClCO) = 1827.246444(20) cm^?1.     

Rotation–torsion analysis of the Si2H6 infrared fundamental ν9, perturbed by excited torsional levels of the vibrational ground state

The lowest infrared active perpendicular fundamental ν₉ of disilane has been analysed on a Fourier transform spectrum between 320 and 430?cm^?1, at the spectral resolution of 0.0012?cm^?1. The rotation–torsion structure of this band is affected by x,y Coriolis interactions with excited torsional levels of the vibrational ground state, correlating with components of 3ν₄ and 4ν₄ in the high barrier limit. The interaction of ν₉ and 4ν₄, forbidden in the D_3d symmetry limit, is allowed between components of E torsional symmetry under the G₃₆(EM) extended molecular group, because of the large amplitude of the internal rotation motion. We could determine the values of the main vibration–rotation–torsion parameters of ν₉, interaction parameters, and the vibrational wavenumbers of the four torsional components of 3ν₄ and of the E_3d component of 4ν₄. The intrinsic torsional splitting of ν₉ is found to be smaller than in the ground vibrational state by 0.0066?cm^?1, in good agreement with our theoretical predictions. The possibility of observing the effects of D_3d-forbidden interactions in the spectra of ethane-like molecules is also discussed.     

High-resolution infrared spectrum of hydrogen peroxide: The ν6 fundamental band

The infrared spectrum of the ν₆ asymmetric deformation band of hydrogen peroxide (H₂O₂) was studied in the region 1100–1350 cm⁻¹ using the two techniques of Fourier transform spectroscopy at 0.02 cm⁻¹ resolution and tunable diode laser spectroscopy at Doppler-limited resolution. Details of the wavelength calibration procedures adopted are discussed. For the first time, accurate values of the molecular parameters of this torsionally doubled, vibrational band were obtained. A total of 708 assigned transitions have been analyzed to yield a set of 14 rovibrational constants for the lower torsion-vibration level (SD = 0.00487 cm⁻¹) and 13 rovibrational constants for the upper torsion-vibration level (SD = 0.00382 cm⁻¹). These hybrid bands are primarily A type with band centers at 1264.5812 ± 0.0009 and 1273.6830 ± 0.0009 cm⁻¹. Because of the absence of observed perturbations, the derived molecular constants can be used to calculate transition frequencies with a high degree of accuracy up to K_a = 6.     

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.     

High resolution FTIR study of the ν5 and ν6 bands of CH2D35Cl: analysis of resonances and determination of ground and upper state constants

The isotopically pure form of methyl chloride, CH₂D³⁵Cl, was synthesized and investigated by Fourier transform infrared spectroscopy with an unapodized resolution of 0.004?cm^?1 in the range 650–900?cm^?1, the region of the lowest fundamentals ν₅ (827?cm^?1) and ν₆ (714?cm^?1). These distinct bands have been analysed in detail in the P-, Q- and R-branches. In spite of their expected a/b-hybrid nature, both envelopes show the peculiar characteristic of only a-type bands of near prolate asymmetric top molecules. Ground state parameters have been determined for the first time through ground state combination differences from both bands. Parameters of the excited vibrational states and coupling constants have been obtained using a model which accounts for c-type Coriolis interaction and ΔK_a?=?±?2 anharmonic resonance.     

High resolution IR spectrum of the ν8 band of CH2DF: analysis of the interactions with the near vibrational levels

The IR spectrum of the ν₈ band of monodeutero methyl fluoride has been recorded with a resolution of 0.004 cm^?1 using a Fourier transform spectrometer. The ν₈ vibration, of A′′ symmetry species, gives rise to a pure c-type envelope centred at 1298.58 cm^?1, resembling a perpendicular band of a prolate symmetric rotor. From the spectral analysis it has been found that ν₈ is coupled with ν₄ for the low K_a sublevels while for the higher ones other vibrational states, directly or indirectly, are also interacting. For satisfactory reproduction of the rovibrational data of ν₈, the Watson's Hamiltonian in the I^r representation has been implemented with interaction parameters, which included first- and second-order a-, b-type and c-type Coriolis couplings with ν₄ and ν₉, respectively. Being these states also interacting with other levels, the effective spectroscopic parameters of the analysed band up to fourth order have been obtained from a data set formed by the six fundamentals located below 1500 cm^?1.     

The high-resolution infrared spectrum of Si2H6: rotation–torsion analysis of the ν5 and ν7 fundamentals,and torsional splittings in the degenerate vibrational states

The infrared active ν₇ and ν₅ fundamentals of disilane, coupled by an x,y Coriolis interaction, have been analysed on a Fourier transform spectrum between 2120 and 2225?cm^?1, at the Doppler limited spectral resolution. A Fermi resonance with 2ν ₂?+?ν₉ affects the Δ K?=?1 side of ν₇, and both ν₇ and ν₅ show the effects of several additional localized perturbations. Line splittings in the ν₅ transitions are not observed, showing that the torsional splitting in the ν₅ excited state and in the vibrational ground state are almost equal. The intrinsic torsional splitting of ν₇ is found to be smaller than in the ground vibrational state by 0.0085?cm^?1. This splitting value and those found for the other two infrared active degenerate fundamentals, ν₈ and ν₉, follow the trend expected from our theoretical predictions. Exploratory numerical calculations show that the decrease of the torsional splittings, observed in the fundamental degenerate vibrational states of disilane, can actually be accounted for by the head–tail and torsional Coriolis coupling of all the degenerate vibrational fundamentals, in several torsional states.     

First high-resolution analysis of the ν1, ν3 and ν1 + ν3 bands of sulphur dioxide 33S16O2

• High-resolution spectra of ³³S¹⁶O₂ have been recorded for the first time in the 8 and 4 µm spectral regions.

• The ν₁, ν₃ and ν₁ + ν₃ bands of the ³³S¹⁶O₂ have been analysed up to very high quantum numbers.

• Accurate ro-vibrational upper states constants have been determined.

     

Sub-Doppler laser-Stark and high-resolution Fourier transform spectroscopy of the ν3 band of formic acid

The 5.6-μm band of HCOOH, which is the strong carbonyl stretch mode, is analyzed using a combination of sub-Doppler resolution laser-Stark data obtained with a CO laser and Fourier transform data obtained from a Bomem interferometer. The Fourier transform data, including 647 lines with J′ ≤ 22 and K_a ≤ 11, are fit with a Watson-type Hamiltonian to determine excited state constants. The Coriolis interactions with v₅₊₉ and v₆₊₉, previously noted by Kuze et al., are included in the analysis; the former by using an exact diagonalization technique, the latter via perturbation theory. Taking the molecular parameters from this fit, the laser-Stark data are then analyzed to give ground and excited state dipole moments, yielding the following results in Debyes: μ″_a=1.4071(8)μ″_b=0.227(10)μ′_a=1.4353(9)μ′_b=0.214(9), where the errors are 3σ estimates. The laser-Stark data are limited to J′ ≤ 7 and give a ± 14 MHz fit to 191 lines.     

A simultaneous analysis of ν5, ν6, and the ground state of hydrazoic acid

The pure rotational spectrum in the vibrational ground state [J. Bendtsen and F. M. Nicolaisen, J. Mol. Spectrosc. 119, 456–466 (1986)] and the infrared spectrum of the fundamental bands ν₅ and ν₆ [J. Bendtsen, F. Hegelund, and F. M. Nicolaisen, J. Mol. Spectrosc. 118, 121–131 (1986)] of HN₃ have been simultaneously analyzed using a three-level model taking into account resonance between the ground state and ν₅ due to centrifugal distortion [K. Yamada, J. Mol. Spectrosc. 81, 139–151 (1980)] and a- and b-Coriolis interactions between ν₅ and ν₆. A set of ground- and upper-state constants have been obtained and values for the centrifugal distortion parameter C₅^ab and the Coriolis coupling constant ζ_5,6^b are derived. A complete set of ground-state energies for J ≦ 50 and K_a ≦ 10 is tabulated.     

A high-resolution infrared study of the ν4 band of CH3I

The infrared spectrum of the ν₄ band of CH₃I around 3060 cm⁻¹ was studied at a resolution of 5.4 × 10⁻³ cm⁻¹. About 1850 transitions were assigned. The K range was from KΔK = −7 to KΔK = +9 and the highest J values were about 75. The anomalous rotational structures observed in the subbands ^PQ₆ and ^RQ₅ – ^RQ₇ were explained as a consequence of Coriolis and Fermi resonances with combination levels. The standard deviation of the least-squares fit with 19 parameters was 0.00083 cm⁻¹. In addition to the fundamental band, the hot band ν₃ + ν₄ − ν₃ was also studied.     

Laser stark spectroscopy of the ν2 fundamental band of 15NH3

The ν₂ fundamental band of ¹⁵NH₃ has been observed with a laser Stark spectrometer in Doppler-limited resolution. A set of 38 band constants including the electric dipole moment and its rotational dependence are determined from 416 Stark resonances observed in the present work and three submillimeter lines reported in the literature. The ν₂-band absorption line frequencies in the region 800–1160 cm⁻¹ and their relative absorption intensities are estimated from the band constants.     

High-resolution Fourier transform study of the ν3 fundamental band of trans-formic acid

Using high-resolution Fourier transform spectra of trans-HCOOH recorded at 5.6 μm, we carried out an extensive analysis of the strong ν₃ fundamental band (carbonyl stretching mode) at 1776.83 cm^?1, starting from results of a previous analysis [Weber WH, Maker PD, Johns JWC, Weinberger E. J Mol Spectrosc 1987; 121: 243–60]. As pointed out in the literature, the ν₃ band is significantly perturbed by resonances due to numerous dark bands. We were able to assign series belonging to the ν₅+ν₇, ν₅+ν₉, ν₆+ν₇ and ν₆+ν₉ dark bands, located at 1843.48, 1792.63, 1737.96 and 1726.40 cm^?1, respectively. The model used to calculate energy levels accounts partly for the observed resonances, and enabled us to reproduce most of the observed line positions, within their experimental uncertainties. We also determined absolute line intensities with an accuracy estimated to 15%. Finally, we generated, for the first time, a list of line parameters for the 5.6 μm region of trans-formic acid.     

A new analysis of the ν2 fundamental band of H2O^＋＊

This paper reports that the absorption spectra of H2O^＋ have been measured by tunable mid-infrared diode laser spectroscopy in the spectral range of 1100-1380 cm^-1. The H2O＋ ions are generated in an AC glow discharge of the gaseous mixtures of H2O/He and detected with the velocity modulation technique. Forty new lines are assigned to the ν2 fundamental band of H2O^＋ （X^2B1）. The observed lines together with other data published previously are fitted to the standard effective Hamiltonian of an asymmetric top, yielding a set of improved rotational constants, spin-rotation constants and their quartic and sextic centrifugal distortion constants for the ν2=1 vibrational state of H2O＋.     

The infrared spectrum of carbon suboxide in the ν6 fundamental region: Experimental observation and semirigid bender analysis

The infrared spectrum of carbon suboxide, C₃O₂, was measured at high resolution in the region from 500 to 600 cm⁻¹. The spectrum was recorded with a Bomem interferometer at a resolution of about 0.004 cm⁻¹; after deconvolution a resolution of about 0.002 cm⁻¹ was attained. Seven bands were identified and assigned to rovibrational transitions of ¹²C₃¹⁶O₂. These consist of the ν₆ fundamental band and some of the hot bands associated with the ν₇, 2ν₇, and 3ν₇ states. The data obtained on the ν₆ + nν₇ states were used as input for a semirigid bender fit yielding the effective CCC bending potential energy function in the ν₆ state together with a number of related parameters. From the results of the present work together with the results of previous semirigid bender fits it was found that C₃O₂ is bent at equilibrium with an equilibrium CCC bond angle of 156° and a barrier to linearity of 28 cm⁻¹.     

FTIR spectra and rovibrational analysis of parallel bands involving the ν1, ν2, and ν3 levels of natural and monoisotopic FClO3

Fourier Transform infrared spectra of gaseous natural FClO₃ and monoisotopic F³⁵ClO₃ have been recorded at 293 and 225 K with a resolution of 0.04 cm⁻¹. Rotational J structure and, in part, K structure were resolved for the parallel fundamentals, combination bands, and overtones ν₁, ν₂, ν₃, ν₁ + ν₂, ν₁ + ν₃, ν₂ + ν₃, 2ν₁, 2ν₂, and 2ν₃. Band origins ν₀, anharmonicity constants χ_ij, and vibration-rotation interaction constants α_i^A and α_i^B have been determined. For F³⁵ClO₃, ν₀ values are ν₁ = 1063.238(6), ν₂ = 716.814(6), and ν₃ = 549.877(3) cm⁻¹. No perturbation was found at the present level of accuracy.     

High-resolution spectroscopy of difference and combination bands of SF6 to elucidate the ν3 + ν1 − ν1 and ν3 + ν2 − ν2 hot band structures in the ν3 region

The strong infrared absorption in the ν₃ S–F stretching region of sulphur hexafluoride (SF₆) near 948 cm^?1 makes it a powerful greenhouse gas. Although its present concentration in the atmosphere is very low, it is increasing rapidly, due to industrial pollution. The ground state population of this heavy species is only 32% at room temperature and thus many hot bands are present. Consequently, a reliable remote-sensing spectroscopic detection and monitoring of this species require an accurate modelling of these hot bands. We used two experimental set-ups at the SOLEIL French synchrotron facility to record some difference and combination bands of SF₆: (1) a new cryogenic multiple pass cell with 93 m optical path length and regulated at 163 ± 2 K temperature and (2) the Jet-AILES supersonic expansion set-up. With this, we could obtain high-resolution absorption spectra of the ν₃ ? ν₁, ν₃ ? ν₂, ν₁ + ν₃ and ν₂ + ν₃ bands at low temperature. These spectra could be assigned and analysed, thanks to the SPVIEW and XTDS computer programs developed in Dijon. We performed two global fits of effective Hamiltonian parameters. The first one is a global fit of the ground state, ν₂, ν₃, ν₃ ? ν₂, ν₂ + ν₃, 2ν₃ and 2ν₃ ? ν₃ rovibrational parameters, using the present spectra and previous infrared, Raman and two-photon absorption data. This allows a consistent refinement of the effective Hamiltonian parameters for all the implied vibrational levels and a new simulation of the 2ν₃ + ν₂ ? ν₂ hot band. The second global fit involves the present ν₃ ? ν₁ and ν₁ + ν₃ lines, together with previous ν₁ Raman data, in order to obtain refined ν₁ parameters and also ν₁ + ν₃ parameters in a consistent way. This allows to simulate the ν₃ + ν₁ ? ν₁ hot band.