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.     

Coherence-converted population transfer FTMW-IR double resonance spectroscopy of CH3OD in the OD-stretch region

Rotationally selected infrared spectra of jet-cooled CH₃OD have been recorded and analyzed in the OD-stretch region (2710-2736 cm⁻¹). The observed spectra are obtained by monitoring three E-species microwave transitions (1₋₁ ← 1₀ at 18.957 GHz, 2₋₁ ← 2₀ at 18.991 GHz, and 3₋₁ ← 3₀ at 19.005 GHz) in a narrowband cavity Fourier transform microwave spectrometer, using the background-free coherence-converted population transfer technique. Of the four upper state subbands observed, two (K′ = 0 and −2) are split by perturbations. The E-species deperturbed band origin is at 2718.1 cm⁻¹. The deperturbed reduced term values follow a pattern similar to the ground state. This allows the J′ = 0 torsional tunneling splitting to be estimated as 2.1 cm⁻¹, which can be compared to 2.6 cm⁻¹ in the ground state.     

Vibrational and Rotational Spectroscopy of 13CD3OD

We have used Fourier Transform spectral data on the C-O stretching mode of ¹³CD₃OD in order to perform a vibro-rotational analysis for this molecule. We have estimated a few molecular parameters of the ground and C-O stretching vibrational modes. Based on these parameters, and by using the Kwan-Dennison model, we propose assignments for a number of far-infrared laser transitions of ¹³CD₃OD.     

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.     

Far-infrared absorption spectra of water vapor H216O and isotopic modifications

Far-infrared absorption spectra of H₂¹⁶O, H₂¹⁸O, H¹⁶OD, H¹⁸OD, D₂¹⁶O, D₂¹⁸O have been observed between 10 and 40 cm^?1 at a resolution of 0.07 cm^?1. Experimental and calculated line positions agree within the accuracy of the experiment (±0.003 cm^?1). The relative intensities of type a and type b transitions of H¹⁶OD and H¹⁸OD are used to estimate the ratio $\text{μ}{}_{\mathrm{a}}\text{μ}{}_{\mathrm{b}}$.     

Tunable laser Stark-difference spectra of CD3OH

We present Doppler resolution limited spectra of the P(J) and R(J) multiplets for J ≦ 10 of the 10-μm CO stretch band of ¹²CD₃¹⁶OH using a tunable diode laser. Relative frequencies within the multiplets accurate to ±0.0002–0.0005 cm^?1 are obtained, but no absolute frequencies are given. We are able to assign most of the hindered rotation and K substructure in these multiplets. The assignments are based on analyses of Stark-difference spectra combined with the ground-state microwave data and the intensity variations which are expected theoretically. The ground and excited state A, K = 1 asymmetry splitting parameters are measured to be δ₁″ = (8.5450 ± 0.0080) × 10^?3cm^?1 and δ₁′ = (9.7706 ± 0.0080) × 10^?3cm^?1, respectively. The ground-state value agrees well with the microwave results. A rapid-scan system for recording data and a computer-aided technique for calibrating and plotting the spectra are described.     

Vibrational spectra and force constants of symmetric tops: ν1, ν5, and 2ν5 of CF335Cl and CF337Cl

The gas phase infrared spectra of CF₃³⁵Cl and CF₃³⁷Cl have been recorded in the ν₁ region and 2ν₅ regions with a resolution of 0.09 cm^?1. Additionally the ν₅ fundamental of CF₃Cl, with natural isotopic abundance, has been reinvestigated with a resolution of approximately 0.36 cm^?1. Molecular constants have been evaluated from the observed spectra by means of polynomials and band contour simulation. The possibility of a Fermi resonance between ν₁ and 2ν₅ is discussed.     

Infrared spectra of AlF3 in solid argon

Three infrared absorptions are assigned to AlF₃ isolated in solid argon: ν₂ = 286.2 cm^?1, ν₃ = 909.4 cm^?1, and ν₄ = 276.9 cm^?1. The multiplet pattern previously reported near 950 cm^?1 is not present in carefully isolated AlF₃. Our spectra do not conclusively rule out a pyramidal structure for AlF₃; however, no infrared absorptions can be confidently assigned to ν₁, the symmetric stretch.     

The millimeter-wave spectrum of perdeuterated methanol, CD3OD

In order to provide accurate rest frequencies for astronomical searches, the spectrum of perdeuterated methanol, CD₃OD, has been measured in the frequency range 62-233 GHz. A total of 379 lines was measured from rotational states up to J=20 and K=10 within the ground and first excited torsional states (v_t=0 and 1). Using a one-dimensional torsion-rotation Hamiltonian, the lines were fitted to measurement accuracy (<30 kHz).     

X-ray spectroscopic studies of the electronic structure of the oxyanions NO 2−, NO 3− and CO 32−

Using synchrotron radiation for excitation, the K-emission spectra of nitrogen and oxygen in NO ₂^? and NO ₃^?, and of carbon and oxygen in CO ₃^2? were measured. The X-ray spectra together with available photoelectron spectra permit a precise positioning of the occupied orbitals of the anions. The intensities of the X-ray spectra provide information on the atomic orbital composition. In general the agreement between the experimental results and those of MO-calculations is satisfactory; in some cases, however, there are considerable discrepancies.     

The infrared spectra of SiH3F: ν3 and ν4 bands

Infrared spectra of silyl fluoride were recorded at a resolution of 0.06 cm^?1 using a Nicolet Fourier transform interferometer. Analyses of the ν₃ and ν₄ bands are presented for ²⁸SiH₃F, together with work on ²⁹SiH₃F, ³⁰SiH₃F, and various hot bands.     

The ν3 band of CD3I around 500 cm−1

The region of the lowest fundamental band ν₃ of CD₃I around 500 cm^?1 is studied at a resolution of 0.015 cm^?1. The K structure in the parallel band ν₃ is resolved for K = 6 – 14. Molecular constants for the ν₃ level are derived, including α₃^A = 3.055(13) × 10^?3 cm^?1. The “hot” band 2ν₃-ν₃ is also investigated.     

Determination of A0 from the ν4 Raman band of CD3Br

The principles and methods of determining A₀ from the Raman spectra of degenerate fundamentals of C_3v molecules are outlined, and applied to the ν₄ band of CD₃Br to yield a value of A₀ = 2.6004 ± 0.0010 cm^?1.     

Vibrational spectra and force constants of symmetric tops: Rotational analysis of ν3 and 2ν3 of H3Si35Cl and H3Si37Cl

The gas-phase infrared spectra of natural and ³⁵Cl isotopically enriched H₃SiCl have been recorded with a resolution of 0.04 cm^?1 in the regions of ν₃ (～550 cm^?1) and 2ν₃ (～1100 cm^?1). The fundamentals of species with ²⁸Si, ²⁹Si, ³⁰Si, ³⁵Cl, and ³⁷Cl and several hot bands of the series nν₃ + mν_i ? mν_i (n, m = 1, 2; i = 3 and 6) have been detected. The parameters ν₀, x₃₃, x₃₆, B₀, α₃^A, D_J⁰ and D_J³ were determined by a combination of least-squares analysis of P and R branches resolved into J peaks (J ≤ 90) and a band contour simulation. Possible resonances of nν₃ and (n ? 1)ν₃ + ν₆ are discussed.     

Frequency measurements of some optically-pumped laser lines in CH3OD

The frequencies of four lasing transitions in CH₃OD have been measured to accuracies of a few parts in 10⁷ by comparison with a microwave oscillator near 20 GHz, via a Josephson harmonic mixer. The frequencies were 2058141.8, 1391972.2, 1016897.2, and 980591.6 megahertz (approximate wavelengths 146, 215, 295 and 306 μm).     

The heat capacity of the layer compounds (CH3CH2CH2NH3)2MnCl4 and (CH3CH2CH2NH3)2CdCl4 from 10 K TO 300 K

The heat capacity of the layer compounds tetrachlorobis (n-propylammonium) manganese II and tetrachlorobis (n-propylammonium) cadmium II, (CH₃CH₂CH₂NH₃)₂MnCl₄ and (CH₃CH₂CH₂NH₃)₂CdCl₄ respectively, has been measured over the temperature range 10 K ?T ? 300 K.Two known structural phase transitions were observed for the Mn compound in this temperature region: at T = 112.8 ± 0.1 K (ΔH_t= 586 ± 2 J mol^?1; ΔS_t = 5.47 ± 0.02 J K^?1mol^?1) and at T =164.3 ± (ΔH_t = 496 ± 7 J mol^?1; ΔS_t =3.29 ± 0.05 J K^?1mol^?1). The lower transition is known to be from a monoclinic structure to a tetragonal structure, while the upper is from the tetragonal phase to an orthorhombic one. From comparison with the results for the corresponding methyl Mn compound it is deduced that the lower transition primarily involves changes in H-bonding while the upper transition involves motion in the propyl chain.A new structural phase transition was observed in the Cd compound at T= 105.5 ± 0.1 K (ΔH_t= 1472.3 ± 0.1 J mol^?1; ΔS_t = 13.956 ± 0.001 J K^?1mol^?1), in addition to two transitions that have been observed previously by other techniques. The higher of these transitions(T = 178.7 ± 0.3 K; ΔH_t = 982 ± 4 J mol^?1 ΔS_t = 6.16 ± 0.02 J K^? mol^?1) is known to be between two orthorhombic structures, while the structural changes at the lower transition (T= 156.8 ± 0.2 K; ΔH_t = 598 ± 5 J mol^?1, ΔS_t = 3.85 ± 0.03 J K^?1 mol^?1) and at the new transition are not known. It is proposed that these two transitions correspond respectively to the tetragonal to orthorhombic and monoclinic to tetragonal transitions in the propyl Mn compounds.In addition to the structural phase transitions (CH₃CH₂CH₂NH₃)₂MnCl₄ magnetically orders at t? 130 K. The magnetic contribution to the heat capacity is deduced from the heat capacity of the corresponding diamagnetic Cd compound and is of the form expected for a quasi 2-dimensional Heisenberg antiferromagnet.     

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.     

Analysis of torsional splittings in the microwave spectra of dimethylether,CH3OCH3 and its isotopes,CD3OCH3 and CD3OCD3

The multiplet splitting patterns of microwave transitions in the ground state and the first two torsional excited states of CH₃OCH₃, CD₃OCD₃, and CD₃OCH₃ were analyzed in terms of the semirigid rotor models C_2vF-C_3vT-C_3vT and $\text{C}{}_3\text{F-}\text{C}{}_{\mathrm{3v}}\text{T-}\text{C}{}_{\mathrm{3v}}\text{T}\text{?}$. The following nonzero potential coefficients were obtained for CH₃OCH₃: V₃₀ = V₀₃ = 909.05 ± 0.49 cm^?1, V′₃₃ = 5.06 ± 1.60 cm^?1; for CD₃OCH₃: V₃₀(CD₃) = 897.18 ± 2.41 cm^?1, V₀₃(CH₃) = 910.45 ± 0.33 cm^?1; for CD₃OCD₃: V₃₀ = V₀₃ = 897.00 cm^?1. These results are compared to earlier microwave studies of these molecules.     

Analysis of the ν3, A-type band of C2H3D

The ν₃, A-type band of C₂H₃D centered at 1288.780 cm^?1 has been analyzed up to J = 33 and K_a = 15. The spectral range from 1351 to 1235 cm^?1 was recorded with a grill-spectrometer “type Girard” and with a resolution of 0.06 cm^?1, and a wavenumber precision of about 2 × 10^?3 cm^?1. From 787 identified transitions it was possible to calculate the rotational energies in the ν₃ excited state, and to refine the corresponding set of parameters.     

12C18O2: High-resolution emission spectra in the 4.5-μm region rovibrational transitions 0v′2v3 → 0v′2(v3 − 1), v2 = l

Emission spectra of gaseous mixtures involving isotopic species of CO₂ excited by a dc discharge were recorded under Doppler-limited resolution, using a high-information Fourier Transform Interferometer, in the region 4–5 μm. In this paper are given the results concerning 34 vibrational transitions (Δv₃ = 1), for ¹²C¹⁸O₂. The band centers and the spectroscopic constants for the 39 vibrational levels involved are reported. They reproduce more than 1000 experimental wavenumbers with a RMS of the order of 2 × 10^?5 cm^?1 for the best vibrational transition and less than 3 × 10^?4 cm^?1 for most of the others. From a weighted simultaneous fit of all the experimental wavenumbers belonging to the Σ-Σ transitions, a set of molecular parameters was computed. A good reproduction of the experimental wavenumbers was obtained for all the vibrational transitions except those involving the level v₃ = 9, our conclusion being that a local vibrational perturbation exists for this level.