Intensity measurements in the v4-fundamental of methane

The absolute intensities of all the J-multiplets between R(13) at 1375cm^-1 and P(12) at 1225 cm^-1, in the v₄-fundamental of ¹²CH₄, have been measured at 300°K. Our values are consistent with published band-intensity measurements and also with the theoretical line strength tabulation by Fox. Spectral transmittance computation using a Lorentz line shape with a hydrogen-broadened half-width of 0.075 cm^-1 atm^-1 at 300°K for all the lines in the band is in excellent agreement with our experimental data measured with a spectral resolution of 0.2 cm^-1. Our best estimate for the absolute intensity of the band is 145±8 cm^-2 atm^-1 at STP.     

Electronic and vibrational spectra of MnO2−4 in KBr crystals

Two new features have been observed in the electronic spectrum of KBr crystals doped heavily with MnO^2?₄ ions. The band at 870 nm is assigned to the crystal field transition e → t₂. The band at 600 nm shows a series of vibrational sub-bands at an interval of 740cm^?1 and is ascribed to the coupling between electronic transition and totally symmetric mode of the ion.A line at 830cm^?1, ascribed to totally symmetric mode v₁(A₁), has been observed for the first time in the Raman spectrum. I.R. spectrum of KBr: MnO^2?₄ shows four lines—one due to MnO^2?₄ in Td symmetry and the other three to the split components of v₃(T₂) for MnO^2?₄ in Cs symmetry. I.R. spectrum of KBr: MnO^2?₄: Ca²⁺ shows another s of four lines—one due to MnO^2?₄ in Td symmetry and the other three to the v₃(T₂) mode of the ion in C_2v symmetry. The v₁(A₁) line could not be observed in the i.r. spectra.     

Quantitative laboratory spectra and spectral line parameters for the v2 and v4 bands of PH3 applicable to spectral radiative models of the atmosphere of Jupiter

Quantitative laboratory PH₃ absorption spectra were obtained in the 800–1350 cm^-1 region, at ～0.05 cm^-1 resolution, with gas amounts corresponding to observed PH₃ absorptions in the atmosphere of Jupiter. A compilation of spectral line positions, intensities and ground state energies has been generated for the v₂ and v₄ bands of PH₃. Line-by-line calculations have been compared with the experimental spectra.     

Vibration-rotation energies of harmonic and combination levels in tetrahedral XY4 molecules: Analysis of the 2ν2 and ν2 + ν4 bands of 12CH4

The theory and the extrapolation method described in the previous paper are used to analyze the v₂ = 2 and v₂ = v₄ = 1 levels of ¹²CH₄. In addition to the well-known parameters of the ground, v₂ = 1, and v₄ = 1 states, the computation of energy levels involves only 6 new parameters for 2ν₂ and 13 for ν₂ + ν₄ up to the fourth order of approximation. These parameters have been determined from Raman and infrared data. Forty-four Raman lines observed by Berger in the region from 3060 to 3090 cm^?1 have been assigned to the 2ν₂ band. The standard deviation obtained by fitting 39 of these transitions with the 6 corresponding parameters is 0.025 cm^?1. The calculated frequencies of ν₂ + ν₄ are compared with moderate resolution ir spectra recorded in our laboratory and the recent spectra of Hunt et al. Totally polarized weak Raman lines observed by Berger in the region from 2850 to 2900 cm^?1 have been assigned to the ν₂ + ν₄ band arising through a second-order Coriolis interaction with the ν₁ band. A project of a comprehensive treatment of the energy levels of methane between 2550 and 3650 cm^?1 is discussed.     

High-resolution infrared and microwave spectroscopy of the ν4 and 2ν2 bands of 14NH3 and 15NH3

More than two thousand Stark resonances of the ν₄ and 2ν₂ band transitions of ¹⁴NH₃ and ¹⁵NH₃ were observed at Doppler-limited resolution with a CO laser. Fourier transform infrared spectroscopy on ¹⁵NH₃ is also carried out. Thirty-six new microwave transitions including seven perturbation-enhanced transitions are observed in the v₄ = 1 excited vibrational state of ¹⁴NH₃ and ¹⁵NH₃. Accuracies of all available spectroscopic data on the v₄ = 1 and the v₂ = 2 states are evaluated and analyses of the vibration-rotation spectra are performed. The Coriolis interaction between the closely lying v₄ = 1 a (antisymmetric level) and v₂ = 2 s (symmetric level) states is explicitly included in the analysis. Smaller Coriolis interactions between the v₄ = 1 a and the v₂ = 1 s states and between the v₂ = 2 s and the v₂ = v₄ = 1 a states (i.e., (v₁, v₂, v′₃, v′₄) = (0 1 0⁰ 1¹)) are also taken into consideration. The accuracy in determination of the principal molecular constants is 10^?6. The parameters thus obtained reproduce the frequencies of the vibration-rotation transitions and inversion transitions within the accuracy of 0.0024 cm^?1.     

Microwave electrophysical properties of superionic crystals Ag2HgI4

The paper concerns itself with the investigation results of temperature dependencies of electric conduction and dielectric properties of Ag₂Hgl₄ crystals in the frequency range of 10⁷–7,8·10¹⁰ Hz. The obtained data have shown that in α-phase at T=326 K, the electric conductivity σ is proportional v^0,28 in the frequency range of 10⁷–10⁹ Hz and σ is proporti onal v^0,5 in the range of (1,1–78)·10⁹ Hz. The dependence σ(v) in the range of (1,1–78)·10⁹ Hz may be conditioned by the jumping mechanism of the conductivity and low frequency oscillations of the crystal lattice. It is believed, tha in the σ-phase of Ag₂Hgl₄ a condition of the existence of the ionic polaron is satisfied. The activation energy of the polaron is ΔE_p=0,09 eV.     

The Infrared Spectrum of CCH2: The Bending States up to v4+v5=4

The vibration-rotation spectra of ¹³C monosubstituted acetylene, ¹²C¹³CH₂, have been recorded in the region between 450 and 3200 cm⁻¹ with an effective resolution ranging from 0.004 to 0.006 cm⁻¹. A total of about 5300 rovibrational transitions have been assigned to 53 bands involving the bending states up to v_t=v₄+v₅=4, allowing the characterization of the ground state and of 30 vibrationally excited states. All the bands involving states up to v_t=3 have been analyzed simultaneously by adopting a model Hamiltonian which takes into account the vibration and rotation l-type resonances. The derived spectroscopic parameters reproduce the transition wavenumbers with a RMS value of the order of the experimental uncertainty. Using the same model larger discrepancies between observed and calculated values have been obtained for transitions involving states with v_t=4. These could be satisfactorily reproduced by only adopting, in addition to the previously determined parameters which were constrained in the analysis, a set of effective constants for each vibrational manifold.     

Line assignments and intensities for the ν3 + ν4 − ν4 band of 12CH4

Assignments and Intensities are reported for 886 lines arising from the “hot-band” ν₃ + ν₄ ? ν₄ of ¹²CH₄ at 3.3 μm. These are determined from spectra at 0.01–0.02 cm^?1 resolution that include intensity measurements at reduced temperatures. Energy levels for the v₄ = 1 state through J = 12 are also given based on the ν₃ + ν₄ band assignments of Hunt et al., and the wavenumbers of the hot-band lines.     

Weakly forbidden vibration-rotation transitions ΔR ≠ 0 in CF4 laser

Known spectroscopic data on the 16 μm CF₄ laser are completely explained by considering weakly forbidden ΔR ≠ 0 vibration-rotation transitions. A rich fine structure of the v₂ + v₄ pumping band with specific spectral interval 0.01 + 0.03 cm^-1 has been experimentally observed. The components of this structure have been used for optical pumping of a CF₄ laser by a quasi-single mode continuously tunable high-pressure CO₂ laser.     

Vibrational relaxation in CD4 and CD4-rare gas mixtures

Using the optic-acoustic effect, measurements of the relaxation time were made after exciting the v₄ mode of CD₄. This was done for pure CD₄ and for mixtures of CD₄ with He, Ne, Ar and Kr, the results being 3.9±0.2, 1.8±0.2, 18±2, 70±15 and ? 100 μs at 1 atm, respectively. From the relaxation time dependence on mass as well as from a comparison between results for CH₄ and CD₄ it is concluded that energy transfer takes place via a vibration-rotation-translation (V-R-T) mechanism.Experiments were also conducted to study the most probable deexcitation path from the higher energy mode, v₃, to translation. This was done for CD₄-CD₄ as well as for CD₄-atom collisions. For pure CD₄ deexcitation occurs via the lower energy group (v₂, v₄), while for CD₄ mixtures it may also occur via the higher energy group (v₁, 2v₂, v₂ + v₄, 2v₄).     

The first negative (BΣ→XΣ) system of CO: excitation of higher vibrational levels

Six bands of the B²Σ⁺→X²Σ⁺ system in the ¹²C¹⁶O⁺ molecule were photographed by conventional spectroscopic techniques under high resolution. The 4-7 band was reinvestigated and the 4-6, 4-8, 5-8, 5-9, and 6-10 bands were recorded and analysed for the first time. The rovibronic structure parameters of the individual bands were obtained from their wavenumber data via a non-linear least-squares procedure fit. The effective Hamiltonians of Brown with direct matrix elements given by Amiot et al. [J. Mol. Spectrosc. 87 (1981) 196] have been used. By means of a merge calculations molecular constants B_v, D_v, and γ_v for B²Σ⁺ (v=4-6) and for the X²Σ⁺ (v=6-10) states and six bands origins ν_v^′-v″ of all the six analysed bands were computed for the B→X system.     

Proton spin-lattice relaxation study of the phase transition in TlH2AsO4

Measurements of the temperature and frequency dependence of the proton laboratory and dipolar frame spin-lattice relaxation rates in powdered TlH₂AsO₄ demonstrate that the ⁷⁵As quadrupole resonance frequency changes from v_Q ≈ 38 MHz at T ?T_c to v_Q 〈 10 MHz at T 〉 T_c. The structural phase transition at T_c = 251 K is thus connected with a disordering of the protons in the O–H … O bonds surrounding the AsO₄ groups.     

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.     

The Infrared Spectrum of C2D2: The Bending States up to v4+v5=2

The vibration-rotation spectrum of ¹³C₂D₂ has been recorded in the infrared region between 420 and 1100 cm⁻¹ with an effective resolution ranging from 0.004 to 0.006 cm⁻¹, and in the millimeter-wave region between 68 and 518 GHz. A total of about 1400 rovibrational transitions (66 of which have been measured in the millimeter-wave region) have been assigned to 8 bands with 15 l-vibrational components involving the bending states up to v_t=v₄+v₅=2. The ground state and nine vibrationally excited states have been characterized. All the measured transitions have been analyzed simultaneously by adopting a model Hamiltonian which takes into account the usual vibration and rotation l-type resonances, together with the Darling-Dennison coupling between the v₄=2 and v₅=2 bending states. The derived spectroscopic parameters reproduce the transition wavenumbers with a standard deviation of the fit of the order of the experimental uncertainty.     

The Fundamental Bands in the Infrared Spectrum of Stibine (SbH3)

The infrared spectrum of stibine, SbH₃, has been recorded in the regions between 720 and 1000 cm^-1 and between 1750 and 2020 cm^-1 at a resolution of about 0.004 cm_-1. Rovibrational transitions belonging to the ν₂, ν₄ bending and ν₁, ν₃ stretching fundamental bands have been measured and assigned for both ¹²¹Sb and ¹²³Sb isotopomers. Strong perturbations due to rovibrational interactions have been observed both in the bending and in the stretching bands. Splittings of the K″=3, 6, and 9 lines have been observed and perturbation-allowed transitions with selection rules Δ (k−?)=±3, ± ±6, and ±9 have been also identified. Simultaneous analyses of transitions belonging to the ν₂/ν₄ or ν₁/ν₃ dyads have been performed. The central frequencies of the hyperfine structures of the rotational transitions in the v₂=1 and v₄=1 states, recorded in the microwave region by Fourier transform spectroscopy [H. Harder, C. Gerke, and L. Fusina, J. Chem. Phys.114, 3508-3523 (2001)], have been included in the data set. The theoretical model adopted explicitly takes into account the Coriolis interactions between the v₁=1 (A₁) and v₃=1 (E) and between the v₂=1 (A₁) and v₄=1 (E) states, including also several essential resonances within them.     

Vibration-rotation matrix elements for diatomic molecules; vibration-rotation interaction functions Fv′v (m) for CO

General expressions for the fourth-order vibrational matrix elements are obtained for the transitions v → v′ (v ? v′ v + 4) using a sixth-power internuclear potential and a quartic dipole moment function. The results for the dipole moment coefficients M₀ to M₄ of CO and for some transition moments R^v′_v deduced from a calculation including successively second, third and fourth order perturbation theory are compared.Using the rotational potential function expanded through the cubic term as a perturbation, we have also obtained general expressions for the vibration-rotation matrix elements. The vibration-rotation interaction functions F^v′_v (m) are calculated for the transitions v → v′ (v = 0, 10, 20 and v ? v′ ? v + 4) of CO and the coefficients C, D, E and G of the quartic polynomials fitting these functions are deduced. Taking account of uncertainties in the matrix elements R⁰₀ to R⁴₀, an error estimate for the coefficients of F²₀(m) and F³₀(m) is given.     

Intensity measurements in the 2v3-band of 13CH4 at low temperatures

Absolute intensities of the J-multiplets P(1)-P(8), R(0)-R(7) and of the Q-branch in the 2v₃-band of ¹³CH₄ have been measured at 100, 150, 200, and 296°K. Our intensity data confirm the recent observation by Fox et al. that substitution of the isotope ¹³C for the central ¹²C atom in methane results in significantly different line strengths in the severely perturbed 2v₃-band. Our results at 296°K for the absolute intensities of R(0) and R(1) are in excellent agreement with the values measured by Fox et al.     

Intensity measurements in freon bands of atmospheric interest

The absolute intensities of the i.r. absorption bands, which are located in the atmospheric window region, of CFCl₃ (“Freon-11”) and CF₂Cl₂ (“Freon-12”) have been measured at 300°K. Our best estimates for these parameters are: for CFCl₃ (“Freon-11”), S_v = 635±36 cm^-2atm^-1 (9.2μ band), S_v = 1536±45 cm^-2atm^-1 (11.8μ band); for CF₂Cl₂ (“Freon-12”), S_v = 718±14 cm^-2atm^-1 (8.7μ band), S_v = 1136±22 cm^-2atm^-1 (9.1μ band), and S_v = 1302±40 cm^-2atm^-1 (10.9μ band).