Microwave spectrum of methylene fluoride-d2, CD2F2 in the excited vibrational states

The rotational spectra of ¹²CD₂F₂ in the ν₂, ν₃, ν₄, 2ν₄, ν₅, ν₇, ν₈, and ν₉ states were observed and assigned. Weak Coriolis interactions between ν₃ and ν₇, ν₃ and ν₉, and ν₅ and ν₇ were analyzed using approximate expressions for the rotational energy levels. The resonance between the ν₂ and the ν₈ state was found much stronger, and an effective two-dimensional Hamiltonian with the Coriolis term in the off-diagonal block was set up to analyze the spectra. The effect of the Fermi resonance between ν₃ and 2ν₄ was found to be very small.The ground-state spectrum of ¹³CD₂F₂ was observed and the rotational constants and the centrifugal distortion constants were determined. The data on ¹²CD₂F₂ and ¹²CDHF₂ were also improved very much in accuracy.The Coriolis coupling constants and the differences between two vibrational levels in resonance, which were determined by the analysis of the satellite spectra, are in good agreement with those obtained from vibrational spectra, except for the ν₂ band center, which is revised to 1170.3 cm^?1. The force constants were also checked using the centrifugal distortion constants of ¹²CD₂F₂, ¹³CD₂F₂, and ¹²CHDF₂.     

Laser Stark spectroscopy of thioformaldehyde in the 10-μm region: The ν3, ν4, and the ν6 fundamentals

The ν₃, ν₄, and ν₆ bands of thioformaldehyde, H₂CS, have been studied using the technique of laser Stark spectroscopy. The H₂CS was produced by the pyrolysis of dimethyl disulfide, and the spectrum was observed using a multipass absorption cell. The band origins are ν₃, 1059.2037 cm^?1; ν₄, 990.1866 cm^?1; and ν₆, 991.0149 cm^?1. The band previously assigned as 2ν₆ has been reassigned as 2ν₂, leading to a value of the ν₂ band origin of ca. 1439 cm^?1. Rotational constants and dipole moments of the vibrational states have been determined.     

The 2ν2, ν1 and ν3 bands of D216O. The ground state (000) and the triad of interacting states {(020), (100), (001)}

Three spectra of D₂¹⁶O between 2170 and 3090 cm^?1 have been recorded with a Fourier transform spectrometer having a resolution of about 5 × 10^?3 cm^?1. A careful analysis of the bands 2ν₂, ν₁, and ν₃ has led to a largely extended and more precise set of rotational levels belonging to the vibrational states (000), (020), (100), and (001). From this set, we have then been able to determine improved rotational constants for the ground state (000) and precise vibrational energies, rotational and coupling constants for the three interacting states (020), (100), and (001). The Fermi-type interaction between (020) and (100) as well as the Coriolis-type interactions between (100) and (001) and between (020) and (001) have been explicitly taken into account. Many vibrorotational resonances were detected and are discussed.     

High-resolution infrared spectrum of the ν2 and ν8 bands of CH2D2

A high-resolution infrared spectrum of methane-d₂ has been measured in the C-D stretching band region (2025–2435 cm^?1). Rotational structures of the ν₂ and ν₈ bands have been assigned by use of the ASSIGN-diagram method, and the c-type Coriolis interaction between ν₂ and ν₈ has been analyzed. The band origins, ν₂ = 2203.22 ± 0.01 cm^?1 and ν₈ = 2234.70 ± 0.01 cm^?1, the rotational constants and the centrifugal distortion constants for the two bands, and the Coriolis coupling constant, $\text{∥;ξ}{}_{28}{}^{\mathrm{c}}\text{∥; = 0.182 ± 0.015}\text{cm}{}^{\mathrm{?1}}$, have been determined.     

Analysis of ν2 of H2Se

The infrared absorption spectrum of ν₂ of H₂Se in the region from 885 to 1347 cm^?1 was obtained with a resolution limit of 0.025 cm^?1 on the University of Denver 50-cm FTIR spectrometer system. We have assigned 1604 lines for the six isotopomers of H₂Se, including 25 lines for the H₂⁷⁴Se isotopomer, and have analyzed them using Watson's A-reduced Hamiltonian in the I^r rotational representation. Ground state constants for each of the five most abundant isotopomers were obtained from fits of microwave transitions combined with weighted averaged ground state combination differences formed from the infrared bands (010), (020), (100), and (001). Upper state constants for each of the five most abundant isotopomers were obtained from least-squares fits of the spectral lines of ν₂, keeping the ground state constants fixed to the values determined from our ground state fits. An alternate set of ground state constants together with isotopic mass adjustment constants for all six isotopomers was determined by simultaneously fitting all available microwave transitions and infrared ground state combination differences. Keeping this set of ground state constants fixed, a single set of upper state constants and isotopic mass adjustment constants for the ν₂ band was determined by a simultaneous fit of infrared spectral lines from all six isotopomers.     

Acetylene spectra with a tunable diode laser: (ν4 + ν5)0+−ν41fQ branches of 12C2H2 and 12C13CH2

The rotational structure of the Q branches of the (ν₄ + ν₅)⁰⁺?ν₄^1f bands of ¹²C₂H₂ and ¹²C¹³CH₂ at 13.7 μm has been observed in a natural sample of acetylene by using a tunable diode laser as a source in a high-resolution infrared grating spectrometer equipped with a precision grating drive. Altogether 23 lines from J = 6 to 28 for ¹²C₂H₂ and 15 lines from J = 6 to 20 for ¹²C¹³CH₂ have been identified. The observed full width at half maximum of the resolved lines of these Q branches is very close to the calculated Doppler width. Molecular constants ν₀ + B″, B′ ? B″ ? 2D″, D′ ? D″, and H′ ? H″ have been derived from the measured line positions of the rotational structure.     

The 2ν2 and ν1 bands of HD16O

The 2ν₂ and ν₁ bands of HDO lying in the region 2235–3115 cm^?1 were analyzed using Fourier transform spectra of “pure” D₂O and of H₂OD₂O mixtures. From this analysis, an extended and precise set of rotational levels belonging to the (000), (020), and (100) vibrational states was derived. Using the (000) levels together with the existing microwave data as input in a least-squares fit, it was possible to obtain reliable rotational constants for the ground state of the HDO molecule.     

Fourier transform spectroscopy on the 3ν2, 2ν2 + ν6 and ν3 + ν5 bands of H2CO

Fourier transform spectra covering the range from 1500 to 5400 cm^?1 with 0.02-cm^?1 resolution have been obtained for formaldehyde. A study of the region above 4000 cm^?1 has yielded rotational constants and other asymmetric rotor parameters for three bands: 3ν₂ (ν₀ = 5177.7611 ± 0.0005 cm^?1)2ν₂ + ν₆ (ν₀ = 4734.193 ± 0.004 cm^?1), and ν₃ + ν₅ (ν₀ = 4335.102 ± 0.001 cm^?1). An analysis of the A-type Coriolis interaction between the 2ν₂ + ν₆ state and the unobserved 2ν₂ + ν₄ state has yielded partially deperturbed rotational constants for the 2ν₂ + ν₆ state. Vibration-rotation interaction constants have been obtained for the ν₂ and ν₆ normal modes by combining the present results with those of previous workers.     

Diborane: High-resolution infrared rovibration studies of 10B2D6

Studies of five comparatively unperturbed infrared active bands in the spectrum of ¹⁰B₂D₆ were undertaken with a resolution of ca. 0.05 cm^?1. These comprise three type-A bands (ν₁₇, ν₁₈, and ν₅ + ν₁₅), one type-B band (ν₈), and one type-C band (ν₁₄). Ground-state rotational and quartic centrifugal distortion constants were determined for the first time from a total of over 400 combination differences. Sets of upper-state parameters were determined for all five bands studied, and the effects of a number of minor Coriolis interactions between fundamental vibrations are discussed.     

Line positions and intensities for the ν1 + ν2 and ν2 + ν3 bands of H218O

The intensities of about 90 lines of the ν₁ + ν₂ and ν₂ + ν₃ bands of H₂¹⁸O have been measured using a Fourier transform spectrum of natural water vapor. The constants involved in the rotational expansion of the transformed transition moment operators corresponding to these bands have been determined through a fit of these line intensities. The constants obtained are used to compute the whole spectrum of the ν₁ + ν₂ and ν₂ + ν₃ bands of H₂¹⁸O providing reliable line positions and intensities. For lines involving perturbed levels a comparison is given with the results obtained for H₂¹⁶O and it is shown that the results for one isotopic species cannot be transferred directly to another one.     

The ν2 fundamental vibration-rotation band of T2O

The ν₂ fundamental vibration-rotation band of T₂O vapor has been measured at grating resolution, and the rotational structure has been analyzed. The band center and the values of the rotational constants A, B, and C for the ground state and excited state have been determined. These values are consistent with the data for J through 6, and with extrapolation from H₂O and D₂O.     

Analysis of 2ν2, ν1, and ν3 of H2Se

We have run the high-resolution infrared absorption spectrum of 2ν₂, ν₁, and ν₃ of H₂Se in the region 5.2 to 3.8 μm. We have identified and fitted approximately 520 transitions in 2ν₂, 930 transitions in ν₁, and 620 transitions in ν₃. Included are transitions from the isotopic species containing selenium isotopes 82, 80, 78, 77, and 76. Using Typke's rotational Hamiltonian, we analyzed all isotopic species simultaneously. Ground-state constants were determined from a simultaneous least-squares fit of 879 distinct ground-state combination differences formed from our data and 109 microwave transitions. Upper-state constants were obtained from least-squares fits of our spectral lines analyzing 2ν₂ as a single noninteracting band and analyzing the Coriolis interacting bands ν₁ and ν₃ simultaneously, keeping the ground-state constants fixed.     

The force field and rz structure of Ketene

Recently determined Coriolis coupling constants for H₂ and D₂ Ketene, centrifugal distortion constants for H₂, HD, and D₂ Ketene have enabled 16 of the 19 parameters in the general force field of Ketene to be determined with significance, the ambiguity between the choice of two sets of A₁ and B₁ species force constants being removed. The r₀ structure has been redetermined using the latest values of the rotational constants of H₂, HD, and D₂ Ketene and an r_z structure has been determined for the first time.     

High resolution infrared spectrum of the ν2 + ν3 and ν1 + ν2 bands of ozone

The vibration-rotation bands ν₁ + ν₂ and ν₂ + ν₃ of ozone appearing in the 5.7 μm region have been recorded at a resolution of 0.019 cm^?1 with a SISAM spectrometer. The rotational levels of the (110) and (011) vibrational states have been fitted using a Hamiltonian which takes into account the Coriolis interaction between these two states. The rotational and coupling constants deduced from this study have been used to calculate a list of the vibration-rotation lines which is of interest for high resolution studies of atmospheric spectra in the 1670–1890 cm^?1 region.     

High resolution infrared spectroscopic studies of ethylene-1,1-D2

Rotational assignments in the ν₆ + ν₉ type-A band and the ν₉, ν₆ + ν₁₁, and ν₁ + ν₆ type-B bands of ethylene-1,1-D₂, recorded at a resolution of ～0.03 cm^?1, enable the ground state rotational constants to be determined much more accurately than previously. A significant change in the A₀ constant is noted. All upper states suffer perturbations to their rotational structures. Analyses, excluding the areas of perturbation, still enable the excited state constants to be determined with considerable precision.     

Analysis of FTIR spectra of CH2BrCl; the ν4 and ν5 fundamentals and their hot-bands ν4+ν6−ν6 and ν5+ν6−ν6

The infrared spectrum of isotopically pure CH₂⁷⁹BrCl has been recorded at a resolution of 0.0023 cm⁻¹ (FWHM) in the range 550-800 cm⁻¹ with a Bruker IFS 120 HR Fourier transform spectrometer in Wuppertal. Here we report the full rotational analysis of the ν₄ and ν₅ fundamentals and of the hot-bands ν₄+ν₆−ν₆ and ν₅+ν₆−ν₆. Ground state combination differences were constructed for all bands, yielding improved ground state constants, up to quartic terms, as well as reliable rotational constants for the ν₄, ν₅, and ν₆ states.     

The vibration-rotation spectrum of methinophosphide: The overtone bands 2ν1 and 2ν3, the summation bands ν1 + ν2 and ν2 + ν3, and the difference band ν1 - ν2

The vibration-rotation bands 2ν₁, 2ν₃, ν₁ + ν₂, ν₂ + ν₃, and ν₁ - ν₂ of H¹²CP were recorded and analyzed. These data were combined with previously reported results for this molecule to obtain an improved and extended set of vibrational and rotational constants. All x_ij and γ_ij were calculated except those that require data from a summation band involving ν₁ and ν₃.     

The ν2 + ν4 and 2ν2 isotropic Raman bands of 12CH4

The purely isotropic Raman spectrum of the ν₁ band, the ν₂ + ν₄ band (enhanced through interaction with ν₁), and the 2ν₂ band of ¹²CH₄ was obtained with a spectral resolution of 0.30–0.35 cm^?1 from exposures with different orientations of the linearly polarized exciting light. The ν₂ + ν₄ and 2ν₂ bands show partially resolved rotational structure. The spectra are interpreted in terms of a model which takes explicitly into account vibrational and rovibrational interactions with other vibrational states, using molecular constants determined primarily from infrared spectra. The computed contours are in excellent agreement with the experimental ones and the observed and calculated peak wavenumbers agree within one tenth of the spectral resolution limit, except for a small region near the ν₁ band. The good overall agreement represents an independent check on the overall correctness of the previously reported molecular constants. A detailed discussion is given of the contributions to the intensities of individual transitions from the three transition moment matrix elements, which in an isolated-band model are the intensity parameters of the ν₁, 2ν₄, and 2ν₂ isotropic bands, respectively.     

The high-resolution infrared spectrum of the ν10, ν14, and ν13 bands in allene-1,1-d2

The perpendicular bands ν₁₀, ν₁₄ and ν₁₃ of allene-1,1-d₂, which are located in the region 550–950 cm^?1, have been studied from their infrared spectra at a resolution near 0.0045 cm^?1. High-quality ground state constants have been determined from ν₁₀ and ν₁₃. The three bands are perturbed by a number of Coriolis and vibrational resonances, and rotation-vibrational constants are derived for the ν₁₀, ν₁₄, and ν₁₃ levels using two models to include such interactions. One of them accounts for type-a Coriolis and vibrational resonances between the four levels ν₁₀, ν₁₄, ν₁₃, and ν₉ using the full asymmetric rotor model of Watson. The other model is based on the symmetric top approximation and includes type-b and -c Coriolis interactions with the ν₃ and ν₄ levels, in addition. A preliminary discussion of resonances in the weak ν₉ band and an identification of the hot bands ν₁₁ + ν₁₀ ? ν₁₁, ν₁₅ + ν₁₀ ? ν₁₅, ν₁₁ + ν₁₃ ? ν₁₁, and ν₁₅ + ν₁₃ ? ν₁₅ is also presented.     

Analysis of ν2 of D2S

The infrared spectrum of ν₂ of D₂S was recorded from 740 to 1100 cm^?1 on the University of Denver 50-cm FTIR spectrometer system. We have assigned 655 transitions from D₂³²S and 129 from D₂³⁴S, and have analyzed them using Watson's A-reduced Hamiltonian evaluated in the I^r representation. We used the recently published D₂³²S and D₂³⁴S ground state Hamiltonian constants [C. Camy-Peyret, J. M. Flaud, L. Lechuga-Fossat and J. W. C. Johns, J. Mol. Spectrosc.109, 300–333 (1985)]. Upper state Hamiltonian constants were obtained from a fit of the ν₂ transitions, keeping the ground state constants fixed while varying the upper state constants. The standard deviation of the D₂³²S ν₂ fit is 0.0025 cm^?1. The standard deviation of the D₂³⁴S ν₂ fit is 0.0041 cm^?1.