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.     

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.     

The vibration-rotation spectrum of D12CP in the region of the ν2 band: The spectroscopic constants for the states 0000, 0110, 0200, and 0220 and the bond lengths of the molecule

The vibration-rotation spectrum of DCP has been recorded with a resolution of 0.004 cm^?1 in the spectral region extending from 575 to 475 cm^?1. The fundamental band ν₂ and the “hot” bands from the vibrational level (01¹0) to the levels (02⁰0) and (02²0) have been identified and analyzed. A total of 347 infrared transitions have been measured and their wavenumbers together with 13 microwave or millimeter-wave frequencies have been fit simultaneously to obtain 15 spectroscopic constants including those arising from l-type doubling and l-type resonance. The agreement between the calculated and measured wavenumbers of nonblended lines is usually within 1 × 10^?4 cm^?1. These constants, used in conjunction with the ones previously obtained for the molecule, allow the calculation of the anharmonicity constants x₂₂ and g₂₂ and of the second-order vibration-rotation interaction constants γ₂₂ and γ₁₁. Although many of the γ's are still missing because an insufficient number of bands have been analyzed, the equilibrium bond lengths for the molecule have been recalculated using the improved set of first-order vibration-rotation interaction constants: r_e(CH) = 1.06596(11)Å and r_e(CP) = 1.540452(18)Å.     

Helium and argon line broadening in the ν2 band of CH4

The spectra of the gaseous mixtures CH₄-He and CH₄-Ar were obtained in the spectral region 1400-1750 cm⁻¹ with a resolution up to 0.003 cm⁻¹. Helium and argon pressure broadenings for the vibration-rotation lines of the ν₂ band of CH₄ have been estimated at room temperature for some lines in the P, Q, and R branches. These values were also calculated using the theoretical approach developed by Robert and Bonamy, extended to the case of tetrahedral molecules. The helium data have been found to be in a satisfactory agreement whereas a divergence of calculated and measured broadening coefficients has been evidenced in the case of argon. Simulations of the ν₂ band shapes of methane perturbed by helium have also been performed.     

Laser Stark spectroscopy of methyl cyanide in the 10-μm region: Analysis of the ν4 and ν7 bands,and the ν7, 3ν81 interaction

About 550 Stark tuned resonances of the ν₄ and ν₇ vibration-rotation bands of CH₃CN were measured using ¹²CO₂, ¹³CO₂, and N₂O lasers. These data are combined with 26 microwave measurements and fitted to a model which includes l-type doubling in ν₇, ν₄-ν₇ Coriolis coupling, and ν₇-³ν₈¹ Coriolis and Fermi couplings. The infrared and microwave data can be reproduced with standard deviations of 7 MHz and 40 kHz, respectively. The many vibration-rotation parameters and the dipole moments are determined with great accuracy. A complete list of derived parameters is given in Table I.     

Coriolis interaction between ν4 and ν6 in the infrared spectrum of HCOF

The present work reports infrared gas spectra of the ν₄ and ν₆ perpendicular bands of HCOF. The vibration-rotation bands have been analysed in the rigid symmetric top approximation. The rotational structure is explained in terms of Coriolis perturbations between these fundamentals. Two possible assignments are given for ν₆; the values of the Coriolis coupling constant for both assignments are equal within the accuracy of the experiment.     

Identification of forbidden vibration-rotation transitions in 15NH3

Forbidden Δ|k ? l| = 3 vibration-rotation transitions have been observed in the ν₄ band of ¹⁵NH₃. The analysis of these transitions, together with previously published data on the allowed transitions, has made it possible to determine a set of molecular parameters, including for the first time the rotational constant C as well as the centrifugal distortion constants D_K and H_KKK, which are necessary for the calculation of energy levels. Some weak forbidden transitions in the ν₂ band have also been observed.     

10-μm sub-doppler laser-Stark spectroscopy of methyl chloride: Analysis of the ν6 bands of the CH335Cl and CH337Cl

About 900 Stark transitions from 70 vibration-rotation transitions in CH₃³⁵Cl and about 400 transitions from 38 transitions in CH₃³⁵Cl in the ν₆ band have been assigned. These data were analyzed simultaneously with previously published microwave data on the ν₆ = 1 state. The fit has a standard deviation of about 2 MHz for the data for both isotopes. The isoptopic shift ν₆35 ? ν₆37 = 0.3766(6) cm^?1. Rotational dependence of the dipole moment was also just apparent at about μ_J = μ_K = 1 × 10^?5 D, and a complete set of molecular constants is given.     

Combined subdoppler laser-Stark and millimeter-wave spectroscopies: Analysis of the ν6 band of CH335Cl

The ν₆ fundamental of CH₃³⁵Cl has been remeasured by using a Stark-Lamb-dip technique. These Stark resonances were combined with the zero-field microwave spectra to give determinable combinations of the vibration-rotation parameters and the dipole moments: μ″ = 1.89628(23)D and μ′ = 1.89738(19)D.     

Δk = ±3 “forbidden” infrared transitions in the ν2-band of NH3

Two Δk = ±3 “forbidden” vibration-rotation transitions in the ν₂-band of NH₃ have been measured by using infrared-microwave two-photon spectroscopy and laser Stark spectroscopy. Combining these results with Rao's recent measurement of the band, we have obtained the C₀ rotational constant of 6.2280 ± 0.0008 cm^?1.     

High-resolution FTIR spectroscopy of the 3ν2 band of PH3

High-resolution Fourier transform spectrum of phosphine (PH₃) at room temperature has been recorded in the region of the 3ν₂ band (2730-3100 cm⁻¹) at an apodized resolution of 0.005 cm⁻¹. About 200 vibration-rotation transitions have been least squares fitted with an rms of 0.00039 cm⁻¹ after taking into account the ΔK = ±3 interaction.     

Measurement and analysis of the ν2 bands of 14ND3 and 15ND3

The ν₂ fundamentals of ¹⁴ND₃ and ¹⁵ND₃ have been observed with sufficient resolution to resolve many of the individual P, Q, and R lines for both components of the inversion doublet. With the help of the observed intensity alterations assignments of many of the lines were made. A least-squares analysis was applied to determine the various vibration-rotation constants pertinent for these transitions. The ¹⁴N¹⁵N isotope shift is found to be ?6.2 cm^?1.     

The infrared spectra of 12C32S, 12C34S, 13C32S,and 12C33S

Using a tunable diode laser spectrometer, the infrared absorption spectra of four isotopic species of carbon monosulfide have been observed in the positive column of a dc discharge of CS₂ and Ar. The wavenumbers of 115 vibration-rotation transitions between 1180.5 and 1266.1 cm^?1 have been measured. These lines were assigned to the 1-0, 2-1, 3-2, and 4-3 bands of ¹²C³²S, the 1-0 and 2-1 bands of ¹²C³⁴S and ¹³C³²S, and the 1-0 band of ¹²C³³S. These new data have been combined with the previous infrared and microwave results to determine Dunham coefficients (Y_ij), the Dunham potential expansion constants (a₀,a₁,a₂,a₃, and a₄), and the classical turning points by the RKR method.     

The infrared spectrum of 12C32S and 12C34S

The 2-0 vibration-rotation bands of ¹²C³²S and ¹²C³⁴S near 2530 cm^?1 have been measured with a high resolution spectrometer. The spectroscopic constants for these bands are given, as well as an improved set of Dunham coefficients for the X¹Σ⁺ state of ¹²C³²S.     

Role of intramolecular interactions in Raman spectra of N2 and O2 molecules

The effect of vibration-rotation interactions and anharmonicities on the polarizabilities matrix elements, Raman scattering cross-sections, and depolarization degrees of N₂ and O₂ molecules for vibrational transitions v→v, v+1, v+2, v+3 have been investigated.     

Transition moment,radiative lifetime,and quantum yield for dissociation of the 3Π0+u state of 81Br2

The electric dipole moment of the B → X transition of ⁸¹Br₂ has been calculated from the measured absorption of single vibration-rotation lines with a YAG laser at 558 nm to be |R_e|² = 0.12 D². The corresponding radiative lifetime is τ_rad = 20 μsec. Fluorescence decay times have been measured, as a function of pressure, with a narrowband, nitrogen pumped, dye laser, for vibrational levels v′ = 16, 19, 23. The quantum yield for predissociation at zero pressure is near unity.     

Absorption strength measurement of the ν1 band of methyl chloride

The absorption strengths of the Q-branch manifolds of the ν₁ band of methyl chloride have been measured. The results have been used to deduce the band strength which is 32.1 ± 2.9 cm^?2 atm^?1 at 297 K. The P-branch absorptions have been investigated to determine the possibility of determining a vibration-rotation factor for the band. This factor is 1 + (2αβ + γ) ～ 1.026.     

High resolution infrared measurements on the ν3 vibration-rotation band of SiH4

The ν₃ vibration-rotation band of silane (²⁸SiH₄) has been measured at high resolution (0.030–0.045 cm⁻¹). The tetrahedral splitting has been partially resolved. The analysis of the band has yielded an improved set of molecular constants.     

Rotational transitions in degenerate vibrational states of C3v symmetric top molecules,with application to CH3C15N

General algebraic expressions for the vibration-rotation energy levels and the associated rotational transitions of C_3v symmetric top molecules are developed. These expressions are presented in a convenient form for analysing the spectra of a molecule with any degree of excitation of a degenerate vibrational mode and have been applied to the spectrum of CH₃C¹⁵N.     

Quasi-symmetric top molecule approach to the rotational-vibrational problem of CH3XY molecules: Application to CH3OD

The quasi-symmetric top molecule approach proposed previously [J. Koput, J. Mol. Spectrosc.104, 12–24 (1984)] to calculate vibration-rotation energy levels of a CH₃XY molecule is used to study the COD bending-torsion-rotation energy levels of monodeuterated methanol, CH₃OD. The available 150 transition frequencies (microwave, millimeter wave, and infrared data) have been fitted and the barrier to linearity of the COD skeleton has been found to be about 7000 cm^?1. The effective barrier to internal rotation in the ground state has been determined to be 365.79 cm^?1 and that in the first excited state of the COD bending mode has been predicted to be 380.62 cm^?1.