Diode laser spectra of the ν2 band of 14N16O2: The (010) state of NO2

Diode laser spectra of the ν₂ band of NO₂ are recorded and analyzed. Due to the very high resolution (0.002 cm^?1), the Q branches are completely resolved. Although the whole ν₂ band is not completely covered, the quality of the spectra led to an improved set of rotational and spin-rotation constants. The band center is found to be ν₂ = 749.6541 ± 0.0012 cm^?1.     

Diode laser spectroscopy of the ν11 band of ethylene-d4

The ν₁₁ band of ethylene-d₄ was observed in a region from 2174 cm^?1 to 2227 cm^?1 with Doppler-limited resolution (about 3 × 10^?3 cm^?1) by using a diode laser spectrometer. The ^qP, ^qQ, and ^qR branches with five weak ^sQ lines were analyzed up to K_a = 12 to determine the ground-state as well as the upper-state molecular constants. A Coriolis interaction, possibly a b-type one with the ν₂ + ν₇ band, was found to perturb high-K_a lines. The discrepancy between the observed and the calculated inertia defects in ν₁₁ was explained by the interaction.     

The high-resolution infrared spectrum of ethane-1,1,1-D3 rovibration analyses of the pseudoperpendicular A1A2ν9 + ν10 band and the parallel ν3 + ν4 and ν5 bands

A complete vibration-rotation analysis was made of the A₁A₂ combination band ν₉ + ν₁₀ of CH₃CD₃ at 2582 cm^?1. This band exhibits pseudoperpendicular structure due to the large effective Coriolis interaction constant (ζ ≈ 0.7), which couples the almost degenerate A₁ and A₂ vibrational components for all nonzero values of the rotational quantum number K, and gives a subband Q-branch spacing of 2.5 cm^?1. The location of the band center is assisted through an interruption of the perpendicular-like structure, since both K = 0 Q branches are forbidden by the vibrational and rotational selection rules. The conventional A₁ parallel bands ν₃ + ν₄ at 2507 cm^?1 and ν₅ (CC stretch) at 905 cm^?1 were also analyzed. For ν₅, a combination of numerical analysis and band contour simulation was used to determine a set of upper-state rotation parameters. Combination of the present results with previous data for ν₉ and 2ν₃ permits rotational parameters to be derived for the ν₄ and ν₁₀ fundamentals of CH₃CD₃. Neither of these fundamentals are amenable to straightforward analysis, both being very weak in the infrared and overlaid by the intense ν₁₁ fundamental.     

The infrared spectrum of C3O2: The interaction between ν7 and the ν2 and ν4 vibrations

The 3ν¹₇, 3ν³₇, and 4ν⁰₇ hot bands of the ν₄ fundamental of C₃O₂ in the 1580 cm^?1 region were analyzed from tunable diode laser spectra and the ground state to ν₄ + 2ν⁰₇ band at 1644 cm^?1 from Fourier transform spectra (FTS). The molecular constants for all of the v₄ 1 ← 0 bands as well as the intensity of the ν₀ + 2ν⁰₇ sum band relative to the ν₄ fundamental were in agreement with the predictions of the model of Weber and Ford. FTS spectra at 0.05 cm^?1 resolution were obtained of the sum and difference bands of ν₂ with ν₇ in the 750–900 cm^?1 region. Sharp Q branches occur for each ν₇ state in the sum bands, but only a number of R-branch bandheads and no recognizable Q branches in the difference bands. Assignments of the sum band Q branches through v₇ = 6 were made and molecular constants were determined for the ν₂ + ν¹₇ ← 0 transition at 819.7 cm^?1. The ν₇ potential function in the v₂ = 1 state was found to have a 1.2 cm^?1 barrier with a minimum at α = 4.9°, where 2α is the angular deviation from linearity. The Q-branch positions predicted from the calculated energy levels fit those observed within several cm^?1.     

Vibration-rotation spectra of CH3CN: The ν7 band and its hot bands near 1040 cm−1

Infrared spectra of CH₃CN were measured in the range 170–600 cm^?1 with a Fourier transform spectrometer (0.06 cm^?1 resolution) and several small portions in the range 1020–1065 cm^?1 with a tunable Pb_1?xSn_xTe diode laser spectrometer (0.001 cm^?1 resolution). The ν₇ band was analyzed by taking account of local Fermi resonance with 3ν₈¹, and the following parameters were determined: ν₇ = 1041.8446(15) cm^?1; 3ν₈¹ =1077.88(5) cm^?1; and ∥k₇₈₈₈∥ = 1.98(1) cm^?1. Two hot bands in the ν₇ band region, i.e., (ν₇ + ν₈)² ? ν₈¹ and ν₆¹ ? ν₈¹, were also analyzed, and ν₈ = 365.05(5) cm^?1 and ζ₈ = 0.874(1) were determined by use of the observed transitions of the ν₇ + ν₈ and ν₆ bands.     

Study of the ν2 + ν3 and 2ν6 infrared bands of CH379Br and CH381Br

The rotational analysis of the ν₂ + ν₃ band, centered around 1912 cm^?1, and of both components 2ν₆^±2 and 2ν₆⁰, centered about 1912 and 1904 cm^?1, respectively, has been carried out from a Fourier transform spectrum having a resolution limit of 0.005 cm^?1. A standard deviation of about 0.001 cm^?1 was obtained for about 750 lines of the unperturbed 2ν₆^±2 component for both isotopic species. The ν₂ + ν₃ band, stronger than 2ν₆^±2, is perturbed by two resonances: a Coriolis resonance with the very weak ν₃ + ν₅ band, no line of which has been observed, and an anharmonic resonance with 2ν₆⁰, only four K subbands of which have been observed. For both isotopic species, a standard deviation of about 0.002 cm^?1 has been obtained for about 750 lines of ν₂ + ν₃ and 2ν₆⁰.     

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 region of the 3ν3 band of methane

The spectrum of methane near 9000 cm^?1, the region of the 3ν₃ band, has been recorded at Meudon Observatory with a Fourier transform spectrometer under high resolution. Intensity measurements at two different temperatures, 149 and 295 K, have allowed us to identify two new vibration bands by determining the lower-state quantum numbers J of the transitions. About 100 lines are now assigned in this range, including P and Q branches. Furthermore, the first detailed rotational analysis of the 3ν₃ band has been made; nine parameters of the band have been determined. The standard deviation of the differences between observed and computed wavenumbers for 45 lines of the 3ν₃ band is only 0.045 cm^?1. It is found that the observed 45 lines of the 3ν₃ band correspond to the sublevel l₃ = 3 and C_v = F₂.     

The ν5 and ν3 Raman bands of CH2D2

The ν₅ and ν₃ Raman bands of CH₂D₂ have been recorded with a resolution of 0.35 cm^?1. The ν₃ state is well known from infrared studies. Three hundred twenty-nine transitions of the ν₅ band were analyzed, assuming an unperturbed upper state, giving a standard deviation on the fit of the upper-state energies of 0.037 cm^?1, The constants A, B, C, Δ_J, Δ_JK, and Δ_K differed significantly from the ground-state values, and ν₅ was determined as 1331.41 ± 0.05 cm^?1. This work represents the first complete analysis of the fine structure of a rotation-vibrational Raman band for an asymmetric rotor. The ν₅ state could not be analyzed in infrared so this investigation, once more, demonstrates the usefulness of the Raman method.     

Coherent Stokes and anti-Stokes Raman spectra of the ν1 (A1) and ν2 (E) bands of SF6 and UF6

Coherent Stokes and anti-Stokes Raman scattering are used to study the ν₁ and ν₂ spectral band profiles of UF₆ and SF₆. Most of the observed SF₆ “hot” bands are assigned, leading to evaluations of the anharmonicity constants X_ij: X₁₂ = ?(2.80 ± 0.30) cm^?1, X₁₄ = ?(1.00 ± 0.15) cm^?1, X₁₅ = ?(1.00 ± 0.15) cm^?1. For UF₆, a tentative assignment of the “hot” bands is made: X₁₂ = ?(1.80 ± 0.30) cm^?1, X₁₃ = ?(1.60 ± 0.30) cm^?1, X₁₄ = ?(0.20 ± 0.10) cm^?1, X₁₅ = ?(0.25 ± 0.10) cm^?1, and X₁₆ = ?(0.10 ± 0.05) cm^?1. Parameters such as the vibration-rotation coupling constants are determined. For SF₆: α = (7 ± 2) × 10^?5 cm^?1 for the ν₂ band and α = ?(1.02 ± 0.01) 10^?4 cm^?1 for the ν₁ band. The calculated spectral profiles of the coherent Stokes or anti-Stokes spectra, which are in good agreement with experimental results, give values for the resonant and nonresonant parts of the susceptibility in both molecules. They also show, in some cases, the influence of neighboring combination bands.     

Diode laser spectroscopy of the ν6 band of 13CH3l and the ν″6 band of 12CH2Dl

The ν₆ band of ¹³CH₃I and the ν″₆ band of ¹²CH₂DI have been recorded under Doppler-limited resolution in the region 820–866 cm^?1 using a tunable diode laser spectrometer. For ¹³CH₃I the constants for the ν₆ band were determined by simultaneous analysis of seven ^pQ(J,K) branches and several ^pP(J,K) and ^pR(J,K) transitions. For ¹²CH₂DI, the slight asymmetry introduced by the single D atom gives rise to noticeable asymmetry effects in the spectra of some of the ^pQ(J,K) subbands. From the analysis of six such subbands, the molecular constants for the ν″₆ level were determined.     

Determination of A0 of CH3Br from its Raman spectrum

A value of A₀ = 5.1800 ± 0.0010 cm^?1 for CH₃Br has been determined from an analysis of the ν₄ Raman band, based both on a direct fit of Q-branch frequencies and on ground state combination differences. The constants ν₄, (Aζ)₄, η₄₄, and A_e = 5.2442 ± 0.0015 cm^?1 were also determined. The equilibrium distance of the H atoms from the figure axis is calculated as 0.32077 ± 0.00005 Å. All the fundamental Raman bands of CH₃Br were observed, and experimental results for the ν₁, ν₂ and ν₅ bands are included.     

Diode laser measurements of the band strengths of ν3 and ν6 in 12CH3D

A diode laser spectrometer has been used to measure line strengths for 143 transitions in the ν₆ fundamental band of ¹²CH₃D near 9 μm. These line-strength measurements have been used to derive a band strength for ν₆ and ν₃. The band strength derived for ν₆ is 61.7 ± 1.8 cm^?2 atm^?1, and that for ν₃ is 49.3 ± 1.4 cm^?2 atm^?1 at 395 K.     

Carbon suboxide: The infrared spectrum from 1800 to 2600 cm−1

The infrared spectrum of carbon suboxide has been recorded from 1800 to 2600 cm^?1 at a resolution of 0.003 cm^?1. About 7% of the ca. 40 000 lines observed have been assigned and analyzed, belonging to 36 different bands. Most of these are associated with the fundamental ν₃, at 2289.80 cm^?1, and the combination band ν₂ + ν₄, at 2386.61 cm^?1, each of which give rise to a system of sum bands, difference bands, and hot bands involving the low-wave-number fundamental ν₇ at 18 cm^?1. A few other tentative assignments are made. The bands have been analyzed for vibrational and rotational constants.     

Vibrational spectra and force constants of symmetric tops: High-resolution spectra of H374Ge35Cl in the ν1ν4 region near 2100 cm−1

The gas-phase infrared spectrum of monoisotopic H₃⁷⁴Ge³⁵Cl has been studied in the ν₁, ν₄ region near 2100 cm^?1 with a resolution of 0.008 cm^?1. Rotational fine structure for ΔJ = ±1 branches has been resolved for both fundamentals. ν₁ (a₁), 2119.977 03(19) cm^?1; and ν₄ (e), 2128.484 65(8) cm^?1 are weakly coupled by Coriolis x,y resonance, Bξ_1,4^y 2.6 × 10^?3 cm^?1, and l-type resonance within ν₄, q₄⁽⁺⁾ ?8.4 × 10^?6 cm^?1, has been observed. An extended Fermi resonance with ν₅^±1 + 2ν₆^±2, which mainly affects the kl = ?14 and ?15 levels of ν₄, has been detected and analyzed. In addition, several weak and local resonances perturb essentially every K subband of ν₄ and some of ν₁, and a qualitative model is proposed to account for the features observed in the spectrum. Disregarding the transitions involved in local perturbations, the rms deviation of the fit to the remaining 2021 lines is σ = 1.34 × 10^?3 cm^?1.     

High-resolution infrared spectrum of carbon suboxide: The ν4 + 2ν70 and ν4 + 3ν71 − ν71 bands

The infrared spectrum of the ν₄ + 2ν₇ progression of C₃O₂ has been recorded with a resolution of about 0.018 cm^?1. Two bands of the progression have been completely analyzed. The band centers obtained in this study establish, when combined with previously published experimental results, than 3ν₇¹ is 97.22 cm^?1 above the ground vibrational state.     

Diode laser spectroscopy of the ν6 band of methyl fluoride

The five Q branches, ^PQ₁, ^RQ₀, ^RQ₁, ^RQ₂, and ^RQ₃, of the ν₆ band of methyl fluoride ¹²CH₃F were observed by using a tunable diode laser spectrometer and were analyzed to obtain the following molecular constants (in cm^?1): $\text{ν}\text{?}{}_6\text{= 1182.67605(80)}$, A₆ = 5.2006(14), (Aζ)₆ = 1.5437(11), and (Aζ)₆η_K = 1.6(11) × 10^?4, with 2.5 times the standard errors in parentheses. The precision of the band origin may, however, be 0.001–0.002 cm^?1 because of the wavelength uncertainties of the N₂O spectral lines used as the references. An analysis of the ^RQ₀ subband determined the sign of the q₆ constant to be positive. The α₆^A, α₆^B, and q₆ constants of methyl fluoride are discussed in terms of the anharmonic potential field.     

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.     

Absolute line strengths of 74GeH4 near 5 μm

Line positions and absolute line strengths were measured for 23 Q-branch lines of the ν₃ fundamental of ⁷⁴GeH₄ at 295 K, using an infrared tunable diode laser spectrometer. The spectral range covered was from 2109.9658 to 2110.6218 cm^?1. The average standard deviation of the measured line positions was 0.0006 cm^?1 and that of the line strengths was 3.4%. Vibrational transition dipoles were computed from the measured line strengths, which gave 1226 ± 172 cm^?2 amagat^?1 for the ν₃ integrated band intensity.     

Analysis of the ν2 and ν4 infrared bands of CD4

The infrared spectrum of totally deuterated methane CD₄ has been recorded between 930 cm^?1 and 1180 cm^?1 under high resolution (0.003 cm^?1). The ν₂ and ν₄ bands of ¹²CD₄ have been reanalyzed on the basis of a complete third-order Hamiltonian including all the coupling terms linking the upper states of the two bands. A set of only 16 self-consistent parameters have been adjusted to fit more than 1650 assigned transitions reaching a maximum upper state J value of 20. The obtained standard deviation is 0.0041 cm^?1. In addition, 171 lines of the ν₄ band of ¹³CD₄ have been assigned. They have been analyzed, in the same dyad scheme, by adjusting 7 parameters of the ν₄ band together with the main ζ₂₄ Coriolis parameter. The obtained standard deviation is only 0.0012 cm^?1.