First high-resolution analysis of the ν15, ν12, ν5, ν10 and ν2 bands of oxirane

Fourier transform spectra of oxirane (ethylene oxide, c-C₂H₄O) have been recorded in the 730–1560 cm^?1 (6.4–13.7 μm) spectral region using a Bruker IFS125HR spectrometer at a resolution of 0.0019 cm^?1. A total of six vibration bands, ν₁₅, ν₁₂, ν₅, ν₃, ν₁₀ and ν₂, have been observed and analyzed. The corresponding upper state ro-vibrational levels were fit using Hamiltonian matrices accounting for various interactions. Satisfactory fits were obtained using the following polyads {15¹, 12¹, 5¹} and {10¹, 2¹} of interacting states. As a result, an accurate and extended set of Hamiltonian constants were obtained. The following band centers were derived: ν₀ (ν₁₅) = 808.13518(60) cm^?1, ν₀ (ν₁₂) = 822.27955(37) cm^?1, ν₀ (ν₅) = 876.72592(15), ν₀ (ν₃) = 1270.37032(10) cm^?1, ν₀ (ν₁₀) = 1471.35580(50) cm^?1 and ν₀ (ν₂) = 1497.83309(15) cm^?1 where the uncertainties are one standard deviation.     

High resolution FTIR spectra and analysis of the ν11 fundamental and of the ν2 + ν11, ν5 + ν12 and ν7 + ν16 combination bands of 12C6D6

We report results from measurements of the high resolution FTIR spectrum for the fully deuterated benzene molecule C₆D₆ in the range 450–3500 cm^?1. Accurate spectroscopic constants have been obtained for the fundamental vibration ν₁₁ at 496.208 cm^?1 and improved ground state constants have been deduced from a fit of ground state combination differences. The J structure of the combination parallel bands ν₂ + ν₁₁ (at 2798.1 cm^?1), ν₅ + ν₁₂ (1802.5 cm_?1) and ν₇, + ν₁₆ (2619.3 cm^?1) of C₆D₆ has been analysed as well, from which improved values of the band origin and of the B and D _j constants of the excited states have been obtained. The strongest hot bands accompanying these parallel transitions have been assigned by means of the anharmonic force field calculated by Maslen et al. [1992, J. chem. Phys., 97, 4233]. In particular (ν₁₁ + ν₁₆) ? ν₁₆ is assigned to the band at 492.4 cm^?1 even though its shape is typical of a perpendicular transition (PAPE). New values for the ν₅, ν₁₂ and ν₁₆ band origins are determined from the band origins of combination bands and from calculated anharmonic constants. Numerous anharmonic constants are derived from the assignment of hot band and combination transitions.     

Simultaneous analysis of the ν2 and ν4 bands of methane

Vibration-rotation spectra of the ν₂ and ν₄ bands of CH₄ have been analysed by a simultaneous diagonalization of the hamiltonian matrices for the v ₂=1 and v ₄=1 states coupled by the Bξ_2,4 Coriolis interaction term. The effective hamiltonians used extend to sextic centrifugal distortion terms. The results are a significant improvement on any previous analysis; 438 assigned transitions up to J′=16 have been fitted with an overall standard deviation of 0·016 cm^-1. The method used is compared with an alternative theoretical approach given by Berger.     

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.     

Coriolis perturbations in the ν10, ν7, ν4, ν12 band system of trans-d2-ethylene

The effect of a-, b-, and c-axis Coriolis perturbations in the infrared spectrum of the band system ν₁₀, ν₇, ν₄, ν₁₂ of trans-d₂-ethylene has been studied at a resolution near 0.03 cm⁻¹. From a global analysis of this band system taking into account Coriolis resonances, spectroscopic constants for each of the vibrations are derived as well as second-order Coriolis interaction constants for ν₁₀ and ν₇.     

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.

     

The equilibrium structure of disulfur monoxide: Diode laser spectroscopy of ν1 and ν3 of S218O and ν3 of S216O

Diode laser spectroscopy of ν₁ and ν₃ of ³²S₂¹⁸O and ν₃ of ³²S₂¹⁶O has been carried out and several hundred transition frequencies were measured with a nominal accuracy of ±0.001 cm⁻¹. These data have been combined with earlier microwave and diode laser measurements to produce accurate rotational and distortion constants for the (0, 0, 0), (1, 0, 0), and (0, 0, 1) vibrational states of both isotopic species. These results were combined with microwave data from (0, 1, 0) of both isotopes to allow and equilibrium structure for S₂O to be calculated.     

Stark modulation infrared diode laser spectroscopy of the ν6 + ν8 band of diacetylene

The infrared diode laser spectrum of the ν₆ + ν₈ band of diacetylene (HCCCCH), i.e., a combination band of symmetric π_g (ν₆) and antisymmetric π_u (ν₈) CCH bending vibrations, was recorded by the Stark and source modulation techniques. The analysis of the Stark modulation spectrum allowed us to locate the 2ν₆ (Σ_g⁺) and 2ν₈ (Σ_g⁺) vibrational states, which are inaccessible by infrared transitions from the ground state. It is also shown that the Stark modulation spectrum can be used to confirm the rotational assignment of the ν₆ + ν₈ band.     

Measurements and calculations of H2-broadening and shift parameters of water vapour transitions of the ν1 + ν2 + ν3 band

The water vapour line broadening and shifting for 97 lines in the ν₁ + ν₂ + ν₃ band induced by hydrogen pressure are measured with Bruker IFS 125 HR FTIR spectrometer. The measurements were performed at room temperature, at the spectral resolution of 0.01 cm^?1 and in a wide pressure range of H₂. The calculations of the broadening γ and shift δ coefficients were performed in the semi-classical method framework with use of an effective vibrationally depended interaction potential. Two potential parameters were optimised to improve the quality of calculations. Good agreements with measured broadening coefficients were achieved. The comparison of calculated broadening coefficients γ with the previous measurements is discussed. The analytical expressions that reproduce these coefficients for rotational, ν₂, ν₁, and ν₃ vibrational bands are presented.     

High resolution study of the ν5 + ν12 band of C2H4

The combination band ν₅ + ν₁₂ of ethylene, C₂H₄, has been recorded for the first time with a high resolution Fourier transform spectrometer Bruker IFS 125HR. Assignments of transitions and preliminary rotational analysis are made. Two models (Hamiltonian of the isolated vibrational state and Hamiltonian that takes into account resonance interactions) are used. Influence of the local resonance interactions on the parameters and reproduction power of the models is discussed.     

Analysis of the ν6 band of carbonyl fluoride

The vibration-rotation spectrum of the ν₆ fundamental band of carbonyl fluoride (COF₂) has been recorded at room temperature and 0.005 cm⁻¹ resolution, using a Fourier transform spectrometer. Although the strong Q branch at 774 cm⁻¹ is only partially resolved in the spectrum, most of the K structure of various J subgroups in the P and R branches has been fully resolved. More than 1500 transitions belonging to J values up to 40 have been assigned and simultaneously fitted with the microwave frequencies reported by J. H. Carpenter [J. Mol. Spectrosc. 50, 182–201 (1974)] with a standard deviation of 0.0006 cm⁻¹. By incorporating quartic and sextic centrifugal distortion coefficients in Watson's reduced Hamiltonian in the I^r representation, upper state rotational constants A, B, and C have been determined to an accuracy better than 10⁻⁵ cm⁻¹. Ground state rotational and fourth order centrifugal distortion constants were constrained in the analysis to the values reported by W. Lewis-Bevan et al. [J. Mol. Spectrosc. 113, 458–471 (1985)].     

Diode laser spectroscopy of the ν1 and ν3 bands of thiazyl fluoride (FSN)

The ν₁ (FS stretch) and ν₃ (SN stretch) bands of FSN have been measured with Dopplerlimited resolution using a diode laser spectrometer. An accurate set of band constants were determined for ν₁ from a simultaneous fit to 265 infrared data and 73 ground state rotational transitions. The ν₃ band was found to be perturbed as the result of a Coriolis-type interaction between the states (0, 0, 1) and (1, 2, 0). Further difficulties with ν₃ were produced by the presence of many strong absorption lines from an SO₂ impurity. A limited set of effective band constants were determined for this band. Some general aspects of Q-branch absorption line patterns are briefly discussed.     

Analysis of the stimulated Raman spectrum of the ν16ν2 + ν18 Fermi dyad of benzene

Ionization-detected stimulated Raman spectroscopy was used to obtain high-resolution recordings of the two perpendicular bands of the benzene molecule centered at 1591.327 and 1609.518 cm⁻¹. The effective resolution was further enhanced by deconvolving the spectrum to a linewidth 0.003 to 0.004 cm⁻¹. Fine-tuning of the ionizing radiation made it possible to record the transitions belonging to each band separately, thus greatly simplifying the spectrum in the region of overlap. The strong ^sS and ^oO branches were, for the most part, completely resolved as were many lines in the weaker ^oP and ^sR branches and even in the central ^oQ and ^sQ branches. The observed bands belong to the E_2g fundamental ν₁₆ in nearly exact Fermi resonance with the combination ν₂ + ν₁₈. A detailed rovibrational analysis of the spectrum is reported. A perturbation detected in the ^sS_k branches of the lower-frequency band for K = 19 to 23 was identified as a quintic anharmonic resonance with the third overtone, 4ν₂₀, of the lowest lying fundamental ν₂₀, which is infrared- and Raman-inactive (species E_2u). Deperturbed spectroscopic constants for the interacting states are reported which reproduce the observed line positions with a standard deviation of 0.0013 cm⁻¹. The unperturbed origins of the ν₁₆ and ν₂ + ν₁₈ states are only 1.106 cm⁻¹ apart. The fundamental ν₁₆ was identified with the higher-frequency state with origin at 1600.976 cm⁻¹.     

High-resolution Fourier transform spectroscopy of the ν2 and ν3 fundamentals of nitrosyl fluoride,FNO

The ν₂ and ν₃ fundamentals of FNO have been recorded with a Fourier transform spectrophotometer at an apodized resolution of approximately 0.004 cm^?1. The Fourier infrared data have been analyzed together with previous microwave data to yield improved molecular parameters for the (000) and (010) vibrational states and the first set of constants for the (001) state. The main results (in cm^?1) are

     

16.

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

《Journal of Molecular Spectroscopy》1987,124(2):306-316

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.     

17.

Line intensities for the ν1, ν3 and ν1+ν3 bands of 34SO2     

J.-M. Flaud  W.J. Lafferty  R.L. Sams 《Journal of Quantitative Spectroscopy & Radiative Transfer》2009,110(9-10):669-674

Using both high resolution (0.0018 cm^?1) and medium resolution (0.112 cm^?1) Fourier transform spectra of an enriched ³⁴S (95.3%) sample of sulfur dioxide, it has been possible to accurately measure a large number of individual line intensities for some of the strongest of the SO₂ bands, i.e. ν₁, ν₃ and ν₁₊ν₃. These intensities were least-squares fitted using a theoretical model which takes into account the vibration–rotation interactions linking the upper energy levels where needed, and, in this way, expansions of the various transition moment operators were determined. The Hamiltonian parameters determined in previous analyses together with these moments were then used to generate synthetic spectra for the bands studied and their corresponding hot bands providing one with an extensive picture of the absorption spectrum of ³⁴SO₂ in the spectral domains, 8.7, 7.4, and 4 μm.     

18.

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

《Journal of Molecular Spectroscopy》1986,118(1):288-297

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.     

19.

Analysis of FTIR spectra of CH2 79Br35Cl; the ν3 and ν9 fundamentals     

Marcel Snels  El Bachir Mkadmi 《Molecular physics》2013,111(13):1469-1473

The infrared spectrum of isotopically pure CH₂ ⁷⁹BrCl has been recorded at a resolution of 0.0025?cm^?1 and 0.0023?cm^?1 (FWHM) in the range 600–1600?cm^?1 with a Bruker IFS 120 HR Fourier transform spectrometer in Wuppertal. Here we report the full rotational analysis of the ν₃ and ν₉ fundamentals of the most abundant species CH₂ ⁷⁹Br³⁵Cl . Improved ground state constants, up to quartic terms, have been obtained from ground state combination differences (GSCD) involving transitions of the fundamentals ν₃, ν₄, ν₅ and ν₉. Both ν₃ and ν₉ transitions were fitted to a Watson-type Hamiltonian in the S-reduction, yielding accurate molecular constants for the ν₃ and ν₉ excited states. Small local perturbations were observed in both bands. Prominent features in the spectra were assigned to the ν₃ and ν₉ fundamentals of the CH₂ ⁷⁹Br³⁷Cl isotopic species and the hot-bands ν₃+ν₆???ν₆ and ν₉+ν₆???ν₆ of CH₂ ⁷⁹Br³⁵Cl.     

20.

Study of the ν2 + ν10 Hybrid Band of the Trans-C2H2D2 Molecule     

Ziatkova  A. G.  Giniyatova  A. B. 《Russian Physics Journal》2019,61(12):2300-2304

Russian Physics Journal - The ν2 + ν10 (Bu) hybrid band of the trans-C2H2D2 molecule in the region 2100–2300 cm–1 is studied for the first time. The spectrum has been analyzed...     

	Ground state	$\text{ν}{}_2$	$\text{ν}{}_3$
A	3.1751882 (17)	3.1861249 (12)	3.1958722 (15)
B	0.39508266 (12)	0.39407878 (14)	0.39211484 (14)
C	0.35051504 (11)	0.34899779 (16)	0.34747411 (14)
$\text{ν}{}_0$	0	765.3551 (4)	519.5980 (4)

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.     

Line intensities for the ν1, ν3 and ν1+ν3 bands of 34SO2

Using both high resolution (0.0018 cm^?1) and medium resolution (0.112 cm^?1) Fourier transform spectra of an enriched ³⁴S (95.3%) sample of sulfur dioxide, it has been possible to accurately measure a large number of individual line intensities for some of the strongest of the SO₂ bands, i.e. ν₁, ν₃ and ν₁₊ν₃. These intensities were least-squares fitted using a theoretical model which takes into account the vibration–rotation interactions linking the upper energy levels where needed, and, in this way, expansions of the various transition moment operators were determined. The Hamiltonian parameters determined in previous analyses together with these moments were then used to generate synthetic spectra for the bands studied and their corresponding hot bands providing one with an extensive picture of the absorption spectrum of ³⁴SO₂ in the spectral domains, 8.7, 7.4, and 4 μm.     

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.     

Analysis of FTIR spectra of CH2 79Br35Cl; the ν3 and ν9 fundamentals

The infrared spectrum of isotopically pure CH₂ ⁷⁹BrCl has been recorded at a resolution of 0.0025?cm^?1 and 0.0023?cm^?1 (FWHM) in the range 600–1600?cm^?1 with a Bruker IFS 120 HR Fourier transform spectrometer in Wuppertal. Here we report the full rotational analysis of the ν₃ and ν₉ fundamentals of the most abundant species CH₂ ⁷⁹Br³⁵Cl . Improved ground state constants, up to quartic terms, have been obtained from ground state combination differences (GSCD) involving transitions of the fundamentals ν₃, ν₄, ν₅ and ν₉. Both ν₃ and ν₉ transitions were fitted to a Watson-type Hamiltonian in the S-reduction, yielding accurate molecular constants for the ν₃ and ν₉ excited states. Small local perturbations were observed in both bands. Prominent features in the spectra were assigned to the ν₃ and ν₉ fundamentals of the CH₂ ⁷⁹Br³⁷Cl isotopic species and the hot-bands ν₃+ν₆???ν₆ and ν₉+ν₆???ν₆ of CH₂ ⁷⁹Br³⁵Cl.     

Study of the ν2 + ν10 Hybrid Band of the Trans-C2H2D2 Molecule

Russian Physics Journal - The ν2 + ν10 (Bu) hybrid band of the trans-C2H2D2 molecule in the region 2100–2300 cm–1 is studied for the first time. The spectrum has been analyzed...