The rotation-torsion energy levels of the methanol molecule 12CH3 16OH above the triple potential barrier

A high-resolution spectrum of the methanol molecule has been recorded between 720 and 1000 cm⁻¹ with a long-path Fourier transform spectrometer. Twenty-three torsional subbands have been identified. Analysis of these subbands has led to the first determination of rotational constants for torsional levels with n = 3 or n = 4, lying above the potential barrier. The subband centers combined with microwave and far-infrared data of previous investigators allowed determination of the CH₃ and OH moments of inertia, the barrier height, and the Kirtman perturbation constants.     

Millimeter-wave spectrum and internal rotation of 1-silylpropyne,CH3CCSiH3

Rotational transitions of CH₃CCSiH₃ have been observed in the millimeter-wave region using a computer-controlled source-frequency modulation spectrometer with a 1.8-m-long free space absorption cell. The observed spectrum clearly showed the effect of internal rotation with a small potential barrier. It has been analyzed by calculating the torsion-rotation energies on the basis of torsional wave functions obtained by diagonalizing the torsional part of the Hamiltonian. The least-squares analysis has yielded the rotational constant B = 2068.2817(4) MHz and a few centrifugal distortion constants. The barrier height to internal rotation has been determined to be 3.77(70) cm^?1 from the contour map of the standard deviation. Also, the A rotational constant of the silyl group around the symmetry axis has been estimated by fixing the A constant of the methyl group to the value of CH₃CCH.     

Analysis of the ν2 + ν3 band of 12CH4 and 13CH4

The ν₂ + ν₃ bands of ¹²CH₄ and ¹³CH₄ occurring in the region 4400–4650 cm^?1 have been studied from spectra recorded with a high-resolution Fourier transform spectrometer (resolution better than 0.01 cm^?1). Champion's Hamiltonian expansion, Canad. J. Phys.55, 1802 (1977), is applied to the problem of the two interacting F₁ and F₂ vibrational sublevels of this type of a band. As the P branch of ν₂ + ν₃ is strongly overlapped by neighboring bands, a combination-difference method, adapted to tetrahedral XY₄ molecules has been developed to help assignments of lines. A fit of 700 transitions has been performed using 13 new effective constants in the case of ¹²CH₄. In the case of ¹³CH₄, 532 transitions have been fit to 18 constants. The known parameters, relative to the vibrational ground state and the ν₃ state for both methanes, and the ν₂ state for ¹²CH₄ were fixed throughout. Most of the perturbed levels, up to J′ = 12, are well reproduced and the general agreement between experimental and calculated transitions is satisfactory with standard deviations of 0.047 cm^?1 (¹²CH₄) and 0.041 cm^?1 (¹³CH₄). The results (order of magnitude of obtained (ν₂ + ν₃) parameters and comparison of observed and computed intensities) indicate that the ν₂ + ν₃ band is perturbed by many other bands.     

Analysis of the ν6 band of 12CH3D at 8.6 μm

The ν₆(E) fundamental vibration-rotation band of monodeuteromethane (¹²CH₃D) has been recorded in the spectral range 1033–1270 cm^?1 with a resolution of approximately 0.04 cm^?1. Of the 669 transitions with J′ ≤ 17 identified, 633 have been retained for the determination of the rotational levels in the upper state v₆ = 1. The Coriolis interaction between the v₆ = 1(E) and v₃ = 1 (A₁) vibrational states of ¹²CH₃D results in large A₁A₂ splittings of levels with v₆ = 1 and |K ? l₆| = 0 or 3; the mixing in K and l₆ also gives rise to some ten forbidden transitions observed in the spectra. These effects have been very well explained within the formulation based on the contact transformation method. Values of 15 molecular structure constants of the v₆ = 1 state have been determined from a least-squares analysis of the 633 retained transitions. These constants can be used to estimate values of the upper-state energies up to fourth order, and through them the spectral positions of the 633 retained transitions are reproduced with an overall standard deviation of 0.013 cm^?1, which is within experimental uncertainties.     

Microwave spectrum of CH3OD

The microwave spectrum of CH₃OD has been observed in the frequency region between 14 and 92 GHz. All the ground-state transitions with J ≤ 8 and J = 2 ← 1, a-type transitions in the excited torsional states (v = 1 and v = 2) have been observed. The spectrum has been analyzed and rotational constants, torsional constants, torsion-vibration-rotation interaction constants, and centrifugal distortion constants have been evaluated. The Stark effect measurements have been made and the dipole moment components have been determined as μ_a = 0.833 ± 0.008 D and μ_b = 1.488 ± 0.015 D.     

Rotational and Torsional Analysis of the OH-Stretch Third Overtone in CH3OH

We record double resonance spectra of the 4ν₁ band of jet-cooled ¹³C-methanol using single rotational state selection in the ν₁ fundamental and subsequent promotion of the selected molecules to the fourth vibrational level. We then detect transitions to the final excited states by infrared laser assisted photofragment spectroscopy (IRLAPS). The assigned A symmetry transitions reach upper states with K=0 and 1, and J from 0 to 5. For E symmetry, the transitions reach levels with K in the range −3 to 2 and J from 1 to 7. The rotation-torsional analysis determines a value for the torsional tunneling splitting of 2.8±0.4 cm⁻¹ at v₁=4. In a previous paper (J. Chem. Phys.110, 11 359-11 367 (1999)), we reported a trend of monotonically decreasing tunneling splittings in ¹²CH₃OH for v₁=0, 3, and 6 that we explained by a model that incorporates a linear increase in the torsional barrier height with OH stretch excitation. The ¹³CH₃OH tunneling splitting for the 4ν₁ band is in quantitative agreement with the trend found for ¹²CH₃OH.     

Magnetic hyperfine structure and centrifugal distortion in quadrupole spectra of 12CH3I and 13CH3I

Quadrupole spectra of ¹²CH₃¹²⁷I and ¹³CH₃¹²⁷I in the ground vibrational state have been recorded at high resolution (1–2 KHz) using a radiofrequency-microwave double-resonance spectrometer. The magnetic structure of the quadrupole transitions has been resolved and analyzed. Spin-spin and spin-rotation interaction parameters have been determined, together with accurate values of the quadrupole coupling constants and their centrifugal corrections. Comparison with theory is made by using isotopic relations for the two species of iodomethane.     

New ground state constants of CH3Cl and CH3Cl from global polyad analysis

A global analysis of the infrared spectrum of chloromethane involving the ground state and the 13 vibrational states lying up to 2600 cm⁻¹ was recently achieved using high resolution Fourier transform spectra of pure isotopomers. More than 20 000 transitions (cold and hot bands) for each isotopomer ¹²CH₃³⁵Cl and ¹²CH₃³⁷Cl have been assigned and fitted with a standard deviation of about 3 × 10⁻⁴ cm⁻¹ close to the experimental precison. As part of this global effort, improved ground state constants up to sextic centrifugal distortion terms have been determined for each isotopomer taking advantage of the numerous allowed and perturtation-allowed transitions simultaneously fitted using our global model. The axial constants could be determined from ΔK ≠ 0 combinations arising from rovibrational local resonances within Polyads 3 and 5.     

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.     

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.     

Centrifugal distortion and internal rotation analysis of the rotational spectra of N-methylmethanimine d0 and d5

The ground state millimeter-wave spectra of CH₃NCH₂ and CD₃NCD₂ have been measured. The rotational constants, centrifugal distortion constants, and barrier hindering internal rotation of the methyl group have been determined for both species. For the parent species I_α and ?(i,a) were also obtained, and for the perdeuteriated species the quadrupole coupling constants of ¹⁴N were determined.     

Analysis of the ν3 band of 12CH3D at 7.6 μm

The previously reported (J. Mol. Spectrosc.68, 195–222 (1977)) study of the CH₃D spectrum occurring at 1033–1270 cm^?1 which was mainly concerned with the ν₆ fundamental has now been extended to cover the region 1270–1420 cm^?1. In all, 342 transitions belonging to the ν₃ band are now assigned. Both the ν₃ and ν₆ bands are processed simultaneously taking into account of the Coriolis interaction between them, and the fitting of all the experimental data led to 21 significant spectroscopic constants for the states v₆= 1 and v₃ = 1 of CH₃D.     

Microwave spectrum of CHD2CN and CHD2NC,and the harmonic force field and rz structure of methyl cyanide and isocyanide

The microwave spectra of CHD₂CN and CHD₂NC have been measured from 18 to 40 GHz; about 20 type A and 30 type C transitions have been observed for each molecule. These have been fitted to a Hamiltonian using 3 rotational constants, and 5 quartic and 4 sextic distortion constants, in the I^rS reduction of Watson [in “Vibrational spectra and structure” Vol. 6 (1977)]; the standard error of the fit is 26 kHz. For methyl cyanide the 5 quartic distortion constants have been used to further refine the recent harmonic force field of Duncan et al. [J. Mol. Spectrosc.69, 123 (1978)], but the changes are small. Finally, for both molecules, the harmonic force field has been used to determine zero point average moments of inertia I_z from the ground state rotational constants for many isotopic species, and these have been used to determine an r_z structure. The results are compared with r_s structure calculations.     

Rotation-vibration spectrum of CH3F in the range 2000–2100 cm−1

The spectrum of CH₃F between 2000 and 2100 cm^?1 has been investigated under high resolution (0.025 cm^?1). Three parallel bands have been analyzed: 2ν₃ of ¹²CH₃F for which the rotational K structure has been studied, 3ν₃-ν₃ of ¹²CH₃F, and 2ν₃ of ¹³CH₃F. The band center of the main band 2ν₃ of ¹²CH₃F has been found at 2081.383 cm^?1.     

Infrared-microwave double resonance in CH3OH using a Zeeman-tuned 3.5-μm HeXe laser

Infrared microwave double resonance signals have been observed for CH₃OH using the 3.5-μm HeXe laser line. When microwave transitions in the ground vibrational state are pumped, the double resonance signals are obtained on two infrared transitions v = 1 ← 0 of ν^CH(a′); v = 1, J, K, μ = 4, 2, 1 ← v = 0, J, K, μ = 3, 2, 1, and 4, 3, 1 ← 3, 3, 1. Three weak double resonance signals are due to the collision-induced transitions. Their relative intensities have been explained successfully by using the rate constants of collision-induced transitions which are proportional to the dipole matrix elements between the states involved in the transitions.     

New analysis of the Coriolis-interacting v2 and v5 bands of CH3Br and CH3Br

The and fundamental bands of CH₃⁷⁹Br and CH₃⁸¹Br have been studied by Fourier transform infrared spectroscopy with an unapodized resolution of 0.004 cm⁻¹, corresponding to an improvement of one order of magnitude compared to previous studies. For both isotopomers, some 2427 (2239) lines were newly assigned for the parallel and the perpendicular bands and, in addition, 80 perturbation-allowed transitions were also added. The ground-state axial rotational constants A₀ were redetermined from allowed and perturbation-allowed infrared transitions observed in the v₂ and v₅ bands around the local crossing. The A₀ values obtained for both isotopomers are more accurate but fully compatible with those obtained previously. Using those results, and the variation of the rotational constants with vibration, new accurate equilibrium constants A_e and B_e have been also determined for CH₃⁷⁹Br and CH₃⁸¹Br. The excited states v₂=1 and v₅=1 are coupled by Coriolis-type interactions (Δl=±1,ΔK=±1) and (Δl=?1,ΔK=±2), while the l₅=±1 levels of v₅ interact also through “l(2,2)”-type interaction (Δl=±2,ΔK=±2). The Coriolis coupling term was determined to be for CH₃⁷⁹Br and for CH₃⁸¹Br. All interaction parameters have been determined with higher accuracy, compared to previous studies. A total of 4213 (3704) line positions with J?68(64) and K?16(11) including all available data was fitted using 20 (18) parameters with a root-mean-square deviation of 0.0007 (0.0006) cm⁻¹ for CH₃⁷⁹Br and CH₃⁸¹Br, respectively. Two different but equivalent forms of reduced Hamiltonians with two different sets of constrained constants were successfully applied according to Lobodenko's reduction [J. Mol. Spectrosc. 126 (1987) 159]. The ratio of the transition moments, |d₂/d₅|=1.65, and a positive sign of the Coriolis intensity perturbation d₂×ζ₂₅×d₅ were determined. Therefore, it has been possible to generate an accurate prediction of the whole spectrum between 1200 and 1650 cm⁻¹, including Q branches.     

Infrared spectrum of CO2 in the region of the bending fundamental ν2

The infrared spectrum of CO₂ in the region 540–830 cm^?1 has been studied with a Fourier spectrometer at a resolution of 0.010 cm^?1. In addition to the fundamental ν₂, more than 10 “hot” band transitions of ¹²C¹⁶O₂ have been identified. The rotational constants involved have been derived. Special care has been taken in obtaining accurate constants for the level 01¹0. The ν₂ fundamentals of the isotopic molecules ¹³C¹⁶O₂, ¹⁶O¹²C¹⁸O, and ¹⁶O¹²C¹⁷O have also been observed in a natural sample.     

Microwave spectrum of formic acid and its isotopic species in D, 13C and 18O. Study of Coriolis resonances between ν7 and ν9 vibrational excited states

In the investigation of the 8 → 280 GHz region, 241 and 57 transitions of H¹²COOH and DCOOH, respectively, have been assigned to the ν₇ and ν₉ vibrational states coupled by a strong Coriolis resonance. The numerical analysis based on Watson's theory of centrifugal distortion coupled with the addition of Coriolis interaction allows us to obtain a set of parameters which fits the transitions well. The rotational spectra of the isotopic species HCOOD and DCOOD have also been investigated. In this investigation 55 and 67 transitions have been assigned to the ν₇ and ν₉ vibrational states of these two molecules, respectively. A very weak Coriolis resonance was detected. Two non-rigid independent rotors were thus employed and gave us a set of parameters which fits the transitions quite well. The rotational spectrum of the ground state of H¹²COOH, H¹³COOH, HCOOD, DCOOH, H¹²C¹⁶O¹⁸OH, and H¹²C¹⁸O¹⁶OH have been reinvestigated and a set of improved parameters was obtained for each species.     

Laser Stark spectroscopy of the ν4 band of CH3C15N: Fermi resonance with 3ν83

Laser Stark spectra for the ν₄ band of CH₃C¹⁵N have been measured by using CO₂ and N₂O lasers. Almost 650 resonances have been assigned to about 140 ro-vibrational transitions with J′ ≤ 34 and K ≤ 11. An anomaly of the rotational structure around K = 7 has been proved to be due to a Fermi interaction by analyzing each K subband separately. Observed data have been fitted to a model which includes ν₄-3ν₈³ Fermi coupling by the method of least squares. The standard deviation of observed from calculated frequencies is 4.6 MHz. Molecular constants derived are also listed.     

Single-mode optical pumping and superradiant emission in D2O and CH3F

Superradiant FIR emission in both D₂O and CH₃F has been investigated using a tunable single-mode CO₂ TEA laser as optical pump, and results compared with multimode pumping. The frequency offset of the absorbing transitions has been measured and compared to other work. Estimates of the dipole transition moments were also obtained from saturation broadening data. Fine structure of the CH₃F (Q12, K) lines have been resolved and compared with theory. High quantum conversion efficiencies were observed for several lines in D₂O: 38% (99 μm), 20% (385 μm) and 12.5% (121 μm) and in CH₃F 21% (496 μm).