Anharmonic resonances between the v 1 + v ±1 6, v 3 + v ±1 5 + 2v 0 6 and v 3 + v ∓1 5 + 2v ±2 6 vibrational bands of CH3 79Br

The 22 K sub-bands, belonging to the v ₁ + v ^±1 ₆, v ₃ + v ^± ₅ + 2v ⁰ ₆ and v ₃ + v ^±1 ₅ + 2v ^±2 ₆ rovibrational bands of monoisotopic CH₃ ⁷⁹Br, have been identified. An RMS standard deviation of about 0·020 cm^-1 has been achieved by a least squares fit over 619 lines belonging to these 22 sub-bands. For this purpose, a model taking into account (a) anharmonic resonances between (i) v ₁ + v ^±1 ₆, and v ₃ + v ^±1 ₅ + 2v ⁰ ₆, (ii) v ₁ + v ^±1 ₆ and v ₃ + v ^?1 ₅ + 2v ^±2 ₆ and (iii) v ₃ + v ^±1 ₅ + 2v ⁰ ₆ and v ₂ + 2v ₃ + v ^±1 ₅ and (b) Coriolis resonances between the v ₂ and v ₅ modes, was used.     

l-Resonance effects in the hot bands 3v 5 ← 2v 5, (v 4 + 2v 5) ← (v 4 + v 5) and (2v 4 + v 5) ← 2v 4 of acetylene

In the infrared spectrum of C₂H₂ around the fundamental v ₅, the hot bands starting from the levels 2v ₅, 2v ₄ and v ₄ + v ₅ have been investigated. From the analysis of about 20 different bands, 40 molecular constants describing the bending modes v ₄ and v ₅ have been derived.     

O2 broadening of carbon disulphide 12C32S2 in the v 3 and v 3—v 1 bands

Using a tunable diode laser spectrometer, we have measured O₂ broadening coefficients of ¹²C³²S₂ for 31 lines in the v ₃ fundamental band near 6.5 μm and 12 lines in the v ₃—v ₁ band near 11.4 μm. The collisional halfwidths are obtained by fitting the spectral lines with a Voigt and a Rautian profile. The broadening coefficients of ¹²C³²S₂-O₂ are also calculated from semiclassical theory involving, in addition to electrostatic interactions, successively the atom-atom Lennard-Jones model and a simple formulation for the anisotropic dispersion forces, leading to more satisfactory results.     

The 2v 2, v 1 and v 3 bands of H2 16O

The 2v ₂, v ₁ and v ₃ bands of H₂ ¹⁶O occurring in the region 2930–4255 cm^-1 were studied from a spectrum recorded with a high resolution Fourier transform spectrometer (resolution: 0·005 cm^-1). The set of the observed transitions leads by a least squares method to the determination of very accurate values of the rotational levels belonging to the vibrational states (000), (020), (100), (001). From these levels, using Watson's Hamiltonian, we have obtained respectively 21 and 17 rotational constants for the states (000) and (020).     

High-resolution FTIR spectroscopy of the v11 and v2 + v7 bands of ethylene-d4

The Fourier transform infrared spectrum of the v₁₁ band of ethylene-d₄ (C₂D₄) has been recorded with an unapodized resolution of 0.006 cm^?1 in the frequency range 2150 to 2250cm^?1. The v₁₁ band, with a band centre of about 2201 cm^?1, was found to be perturbed by the nearby v₂ + v₇ band centred at about 2235 cm^?1 by a b-type Coriolis interaction. By fitting a total of 772 infrared transitions of v₁₁ using a Watson's A-reduced Hamiltonian in the I^r representation with the inclusion of b-type Coriolis interaction term, two sets of constants, up to quartic distortion constants for the v₁₁ = 1 state, and principal rotational constants for the v₂ + v₇ = 1 dark state, were derived. The inertia defect of the v₁₁ state was found to be 0.0693 ± 0.0004u Ų.     

Narrow resonances (Δv=2·10−2 cm−1) of multiple-photon IR absorption in ethylene

Narrow peaks of multiple-photon absorption in thev ₇ band of ethylene with the spectral width 0.02 cm⁻¹ and the contrast factor of up to 10² have been observed at the intensity of laser radiation 0.04 and 0.6 MW/cm². The multiple-photon spectra of ethylene in intense IR field have been studied with the use of a quasi-single-mode continuously tunable CO₂ laser. The results of the experiments are interpreted within the model of spepwise molecular excitation due to weak transitions.     

Double resonance and collision-induced transitions in the radiofrequency spectra of H2CO and HDCO observed inside the cavity of a CO2 laser

Many radiofrequency resonances corresponding to transitions between the two components of a K-type doublet in H₂CO and HDCO have been observed using infrared-radiofrequency double resonance inside a CO₂ laser cavity. For strong resonances, additional transitions induced by collisions have also been observed and these provide information on collisional processes. The collision-induced transitions also provide a method for assigning the K doublet frequencies in the ground and v₄ = 1 states of H₂CO, and in the ground, v₅ = 1, and v₆ = 1 states of HDCO; the rovibrational transitions pumped by the CO₂ laser can therefore be determined. The upper state rotational transitions and the infrared frequencies for the transitions in exact coincidence with the CO₂ laser lines provide accurate additional data in the analysis of the conventional infrared spectrum of the ν₅ and ν₆ bands of HDCO. In addition, the 195-μm far-infrared laser line in HDCO, observed by Dangoisse et al. [J. Quantum Electron. QE-13, 730–731 (1977)] has been assigned as the 24_6,19→23_6,18 transition in the v₆ = 1 state.     

The v 3 and 2v 3 I.R. bandshapes and dipole correlation functions of compressed gaseous N2O; intensity measurements of the 2v 3 band

The I.R. spectrum of the ν₃ band (4·5 µm) of N₂O has been studied for temperatures varying from 219 to 298 K and densities up to 85 kg m^-3. The 2v ₃ band (2·3 µm) has been analysed at room temperature for densities up to 182 kg m^-3; measurements of the integrated intensities as a function of density show no evidence of pressure induced absorption. This band has also been observed in the vicinity of the critical region.

The dipole moment autocorrelation function is used to assess a collisional model derived from the impact approximation and the Gordon M- and J-diffusion models developed classically as well as the semi-classical M-diffusion model. The M- and J-diffusion models reproduce well the experimental correlation function for the ₃ band; the semi-classical M-diffusion model is better than the classical ones for the overtone 2v ₃ and gives a satisfactory account of the correlation functions. For the collisional model considered which implies uncorrelated rotational levels, a discrepancy between theoretical and experimental correlation functions and bandshapes becomes noticeable from about 40 kg m^-3 and increases with density.     

High resolution FTIR spectroscopy of CH2DF: analysis of the v 3 and v 4 interacting bands

The high resolution (0.004cm^?1) Fourier transform infrared spectrum of the monodeuterated form of methyl fluoride, CH₂DF, has been recorded and analysed in the v ₃ and v ₄ band region around 1420cm^?1. Both bands, coming from A′ symmetry vibrations, have a/b hybrid character, although in v ₃ the b-type component prevails over the a-type. The rotational structure has been analysed using a dyad model including c-type Coriolis coupling and high order vibrational resonance between these states. Accurate upper state molecular parameters and interaction terms have been obtained by fitting about 3270 assigned transitions to Watson's A-reduced Hamiltonian in the I^r representation. In addition, from a simultaneous fit of ground state combination differences coming from this analysis and 42 literature microwave transitions, an improved and more complete set of ground state constants, including three new sextic centrifugal distortion terms (Φ_JK, Φ_KJ and Φ_K), has been derived.     

Comparative analysis of the v(OD) and 2v 3(H2O) spectral bands of H2O-D2O system under isobaric heating conditions

The results of an investigation of the influence of isobaric heating on distribution of hydrogen bonds in the H₂O-D₂O system on the basis of comparative complex analysis of the v(OD) and 2v ₃(H₂O) spectral bands are presented. In the case of analysis of the band assigned to the 2v ₃(H₂O) overtone, the possibilities of obtaining more detailed information on the influence of external factors on the formation of local water structure widen significantly. In particular, there are noticeable differences in the quality of the obtainable data for these bands, which are especially manifested in their low-frequency regions, which are determined by the presence of strong hydrogen bonds characteristic of H-bonded high order water n-mers.     

Vibration-rotation analysis of the jet-cooled v12, v7 + v8 and v6 + v10 absorption bands of 12C2H4

A Fourier transform interferometer was used to record the slit-jet cooled absorption spectrum of ¹²C₂H₄ between 700 and 2400 cm^?1I, at a spectral resolution of 0.005 cm^?1. Three bands, v₁₂ at 1442.442 70(1)cm^?1, v₇ + v₈ at 1888.978 23(3)cm^?1 and v₆ + v₁₀ at 2047.775832(2)cm^?1, were rotationally analysed. In the case of 7¹8¹, a known Coriolis perturbation mechanism involving the nearby 4¹8¹ (1958.264cm^?1) and 8¹10¹ (1766.391 cm^?1) states was accounted for in the analysis. The latter fitting procedure included 12 levels from the 4¹8¹ state which are observed because lines from v₄ + v₈ borrow intensity from v₇ + v₈. Compared to the literature, significantly improved vibration-rotation constants were obtained for all upper states reported in the present study.     

The rovibrational Raman spectrum of water vapour v 1 and v 3

The OH stretching region in the Raman spectrum of water vapour has been observed and reproduced by computer simulation using rovibrational wave functions derived from the analysis of high-resolution absorption spectra. Relative intensity measurements allow the determination of the depolarization ratio and the ratio of the two non-vanishing second-order irreducible tensor components for v ₁. These quantities have been combined with the literature value for the cross section of this band to calculate the principal cartesian components of the v ₁ derived polarizability tensor. The cross section for the v ₃ vibration was also determined, and these results are considered in terms of the bond polarizability theory.     

High resolution study of the v 7 + v 8 band of ethylene (C2H4) at 1889 cm-1

The v ₇ + v ₈ A-type band of C₂H₄ has been recorded between 1932 and 1847 cm^-1 with a resolution of 0·06 cm^-1. The transitions with K _-1 ? 8> and J ? 2>5 have been assigned. Although slight Coriolis resonances perturb the band, the analysis has been made easy through the use of an elaborate set of asymmetric top computer programmes. The band centre and a set of upper state constants have been obtained. With these constants, 288 observed upper state energy levels have been fitted with a standard deviation of 0·021 cm^-1.

Using very simple expressions, we have predicted all the resonance effects perturbing the levels of ethylene near 2000 cm^-1. This led us to the identification of the v ₄ + v ₈ and v ₈ + v ₁₀ combination bands in low resolution spectra.     

Difference-frequency source for very low optical frequencies spectroscopy: CO2 induced spectra

In a previous paper [1] the manufacturing, development and testing of a coherent submillimetric source was exposed. This source was obtained by difference frequency mixing of two CO₂ TEA lasers.In this present work, are presented the first results obtained with this mounting and concerning the collision induced spectrum of gaseous carbon dioxide at room temperature in the 4–40 cm^–1 region.The absorption coefficient is calculated together with the first coefficients of its development as a function of density.The curves ₂/v ²=f(v) and ₃/v ²=f(v), wherev is the frequency, are presented. They permit the calculation of the virial coefficients.The results are then compared with those determined by an extrapolation in this frequency range, of measurements already made in CO₂ in higher (optical) or lower (microwaves) frequencies.     

Absolute line wavenumbers in the near infrared: 12C2H2 and 12C16O2

40 absolute line wavenumbers in the 3v ₃ band of ¹²C¹⁶O₂ between 6927 cm^?1 and 6989 cm^?1 and 626 absolute line wavenumbers in the near infrared absorption spectrum of ¹²C₂H₂ between 7060 cm^?1 and 9900 cm^?1 have been measured using high resolution Fourier transform spectroscopy. The calibration of the CO₂ line wavenumbers relied on heterodyne frequencies available in the v ₁ + v ₃ band of ¹²C₂H₂ near 6556 cm^?1. The absolute uncertainty of the calibrated CO₂ line wavenumbers is estimated to 0.000 08 cm^?1. The acetylene spectra were calibrated using heterodyne frequencies available in the 2—0 band of ¹²C¹⁶O and the line wavenumbers obtained in the 3v ₃ band of ¹²C¹⁶O₂. The absolute uncertainty of the calibrated acetylene line wavenumbers is estimated to range from 0.0003 cm^?1 to 0.006 cm^?1 for strong to very weak isolated lines. Comparison with absolute line wavenumbers obtained independently at JPL in the 3v ₃ band of ¹²C₂H₂ near 9649 cm^?1, calibrated using absolute wavenumbers available in the 2—0 and 3—0 (near 6350 cm^?1) bands of ¹²C¹⁶O, shows very good agreement. Also, the vibration—rotation constants for the observed upper vibrational states of ¹²C₂H₂ were determined, but without accounting for the perturbations affecting these states.     

High-resolution FTIR spectrum of vinyl chloride: rovibrational analysis of the v 10 and v 11 fundamental bands

The Fourier transform gas-phase infrared spectra of the v ₁₀ and v ₁₁ bands of natural CH₂=CHCl have been measured with a resolution of 0.005 cm^?1 in the frequency range 820–1010 cm^?1. These vibrations of symmetry species A″ give rise to c-type bands and the transitions observed are characterized by δK _a = ±1 and δK _c = 0, ±2. Both J and K structures have been resolved in different subbranches and about 1800 (J ≤ 64, K _a ≤ 13) and 2800 (J ≤ 72, K _a ≤ 14) transitions for the v ₁₀ and v ₁₁ fundamentals, respectively, have been identified for the ³⁵Cl isotopomer. Combined analysis of the assigned data with the available ground state constants allowed the determination of the band origins, rotational and centrifugal distortion parameters for the v ₁₀ = 1 and v ₁₁ = 1 excited states of CH₂=CH³⁵Cl isotopic species. The molecular constants obtained account for slight perturbations in the v ₁₀ vibrational level.     

Detailed vibrational population distributions in a CO2 laser discharge as measured with a tunable diode laser

A tunable diode laser (TDL) operating in the 2150–2350 cm^–1 wavenumber region is used to probe a conventional cw CO₂ laser discharge. Absorption lines in more than 25 different vibrational bands are observed, enabling us to determine absolute vibrational populations inall levels of concern to the dynamics of the 10 m CO₂ laser. Levels in thev ₃ mode of CO₂ as high as 00°9 are monitored, and it is found that anharmonic effects play a significant role in the populations of such levels. Thev ₁ andv ₂ mode populations are also investigated in detail, and it is found that these modes are strongly coupled and maintain a common vibrational temperature under all discharge conditions. The use of a TDL is shown to be a powerful technique for investigating the dynamics of infrared molecular lasers.This work was supported in part by the National Science and Engineering Research Council, Canada     

T/D isotope selectivity in CO2 laser induced multiple-frequency multiphoton dissociation of trifluoromethane-T

Isotope-selective multiphoton dissociation of CTF₃ in the presence of CDF₃ by TEA CO₂ laser is studied. The highest T/D selectivity of 58 was observed at a sample pressure of 2 Torr in the presence of 20 Torr of argon on excitation by the 9P(24) CO₂ laser line. The effect of multiple-frequency irradiation on selectivity is studied in the P and Q branches of the v ₂ absorption band of CTF₃. No improvement in the selectivity is noticed on going from single- to multiple-frequency irradiation. These results are compared with previous multiple-frequency work on the CTF₃/CHF₃ system, and explained in terms of strong spectroscopic interference from ¹³CDF₃ in the present case.     

Spectral considerations in the laser isotope separation of Uranium Hexafluoride

Key spectral features important in the laser isotope separation of Uranium Hexafluoride are reviewed. Specifically the (v ₃+v ₄+v ₆) band lying in the frequency range of the CO₂ laser, the 3v ₃ band which is covered by the CO laser, and the fundamentalv ₃ band of UF₆ are considered. Computer-calculated spectra show that the ternary combination bands (v ₃+v ₄+v ₆) and 3v ₃ are completely dominated by the solid Q-branches of some 300 to 1000 hot bands, but that the fundamentalv ₃ band has structured P-and R-branches with peaks and holes, provided the pressure is below a few torr. Laser isotope separation can be achieved either on the isotope-shifted slopes of the Q-branches envelopes (“Q-slope method”) or on the coincidence of a peak and a hole in the P-or R-branches regions (“peak-hole method”). Room temperature experiments were carried out in 1972/1973, which used a CO₂ laser with an internal U²³⁸F₆ filter tube that forced lasing on what is believed to have been the P-16 line falling on the right-hand Q-slope of the (v ₃+v ₄+v ₆) band of UF₆. With a chemical reaction for final isotope separation, the measurements yielded a U-235 enrichment factor of about 1.1, in agreement with the maximum possible value of 1.5 for Q-slope operation and the fact that a high cut was used.