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 stimulated Raman gain spectrum of the ν1 band of SF6

We report rotationally resolved stimulated Raman gain spectra of the ν₁ band of SF₆. The fundamental band exhibits a rigid-rotor type spectrum that is readily fit with a band origin of Δα = 774.5445 and a single rotational term Δβ = ?1.10376 × 10^?4 cm^?1. We also observed and analyzed the ν₁ + ν₆ hotband with band origin at 774.1820 cm^?1. With an experimental resolution of 0.0024 cm^?1 there is no evidence for centrifugal distortion or tensor splitting in either band, although the ν₁ + ν₆ band does exhibit first-order Coriolis splitting as expected.     

A high-resolution study of the 14.4-μm infrared band of deuterofluoroform

The FT-IR spectrum of the ν₃ parallel band of deuterofluoroform has been recorded at a resolution of 0.0045 cm^?1. Nine independent spectral parameters were determined which reproduce some 650 observed wavenumbers with a standard error of 3 × 10^?4 cm^?1. The constants derived for the ν₃ band are (in cm^?1): ν₀ = 694.2822(3); B₀ = 0.3309321(9); B₃ = 0.3302464(11); α^B = 6.859(10) × 10^?4; α^C = 1.429 × 10^?4; D₃^J = 3.168(3) × 10^?7; D₀^J = 3.188(3) × 10^?7; D_JK³ = 4.766 × 10^?7; D_JK⁰ = 4.864 × 10^?7; and D_K⁰ ? D_K³ = 2 × 10^?10.     

Inverse Raman spectrum of the ν1-fundamental of CF4

We have obtained fully resolved spectra of the ν₁ (Q-branch) band of CF₄ at a pressure of 4 Torr using a variation of stimulated Raman spectroscopy. With an experimental resolution of ≤0.004 cm^?1, no detectable tensor splitting of the rotational levels exists up to J = 55. The spectrum is readily fit with a band origin α = 909.0720 cm^?1 and a single rotational term β ? β₀ = ?3.417 × 10^?1cm^?1. We have also observed an underlying hot band, which we tentatively assign as the ν₁ + ν₂ ← ν₂ transition, with α′ = 909.1997 cm^?1 and (β ? β₀)′ = ?3.405 × 10^?4cm^?1.     

Ethane spectrum between 1940 and 2152 cm−1: Ground state parameters

The absorption spectrum of ethane was recorded between 1940 and 2152 cm^?1 at a resolution of 0.025 cm^?1. Ground state parameters were determined from the principal band in this region, ν₉ + ν₁₂(E_u): B₀ = 0.6630353 cm^?1, D₀^J = 1.0406 × 10^?6 cm^?1, D₀^JK = 2.575 × 10^?6 cm^?1 (standard errors are 7, 8, and 13, respectively, in the last digits quoted). The quoted values are from the analyses of 269 ground state combination differences, the standard deviation of the least-squares analysis was 0.0032 cm^?1.     

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.     

Tunable laser study of the ν10 + ν11 band of cyclopropane

Diode laser measurements of the ν₁₀ + ν₁₁ (l_tot = ±2) perpendicular band of cyclopropane have led to the assignments of roughly 600 lines in the 1880–1920-cm^?1 region. Most of the spectra were recorded and stored in digital form using a rapid-scan mode of operating the laser. These spectra were calibrated, with the aid of a computer, by reference to the R lines of the ν₁ + ν₂ band of N₂O. The ground state constants we obtained are (in cm^?1) B = 0.670240 ± 2.4 × 10^?5, D_J = (1.090 ± 0.054) × 10^?6, D_JK = (?1.29 ± 0.19) × 10^?6, D_K = (0.2 ± 1.1) × 10^?6. The excited state levels are perturbed at large J values, presumably by Coriolis couplings between the active E′(l_tot = ±2) and the inactive A′(l_tot = 0) states. Effective values for the excited state constants were obtained by considering only the J < 15 levels. The A₁-A₂ splittings in the K′ = 1 excited states were observed to vary as q_effJ(J + 1), with q_eff = (2.17 ± 0.17) × 10^?4 cm^?1.     

High-resolution infrared spectrum of CH2D2: The ν9 fundamental band at 8 u̧m

The infrared spectrum of CH₂D₂ has been recorded between 1100 and 1360 cm^?1 with a SISAM-type spectrometer whose resolution limit is about 0.015 cm^?1 in our spectrum. Some lines have been identified as transitions of the ν₃ parallel band of CH₃D. The band center ν = 1236.2786 ± 0.0010 cm^?1 and a set of upper state constants was obtained for the ν₉ band of CH₂D₂. A perturbation was pointed out in ν₉; nevertheless, all frequencies have been fitted with a standard deviation of 3.8 × 10^?3 cm^?1.     

The vibration-rotation HDO absorption spectrum between 8558 and 8774 cm−1

The absorption spectrum of HDO has been recorded in the region 8558–8774 cm^?1 using a high-sensitivity intracavity F₂^?:LiF center laser spectrometer. The absorption sensitivity is 10^?7 cm^?1 and the line-center determination accuracy is about 4 × 10^?2 cm^?1. The spectrum was interpreted and the absorption lines were attributed to the ν₂ + 2ν₃ band of HDO. Energy levels up to J = 12 and rotational and centrifugal parameters of the vibrational (012) state were obtained.     

Charge carrier mobility in crystals of the Pb<Subscript>0.67</Subscript>Cd<Subscript>0.33</Subscript>F<Subscript>2</Subscript> superionic conductor

The frequency (ν = 10^?1–10⁷ Hz) dependences σ(ν) of the conductivity of single crystals of the Pb_0.67Cd_0.33F₂ superionic conductor with the fluorite-type structure (CaF₂) in the temperature range of 132–395 K have been studied. The dependences σ(ν) have been discussed in the framework of the hopping relaxation of ionic carriers, which are mobile anions F^?. From experimental curves σ(ν), the direct-current (dc) conductivity σ_dc and the average charge carrier hopping frequency ν_h have been determined. This has made it possible to calculate the charge carrier mobility μ_mob and charge carrier concentration n _mob in these crystals. At room temperature (293 K), the electrical parameters are σ_dc = 1.6 × 10^?4 S/cm, ν_h = 2.7 × 10⁷ Hz, μ_mob = 2.0 × 10^?7 cm²/(s V), and n _mob = 5.1 × 10²¹ cm^?3.     

Rotational analysis of vibrational polyads in tetrahedral molecules: Line parameters of the infrared spectrum of 12CH4 in the range 2250–3260 cm−1—Theory versus experiment

Experimental and theoretical line parameters of the infrared spectrum of ¹²CH₄ in the range 2250–3260 cm^?1 covering the pentad ν₁, ν₃, 2ν₂, ν₂+ν₄, and 2ν₄ are reported. The individual line strengths are reproduced with a relative precision of 12% comparable to the experimental accuracy. In all, 6499 transitions have been calculated in the spectral region 2250–3260 cm^?1. Their intensities range from 2.5 to 213 000 × 10^?24 cm/molecule. Virtually all the absorptions of ¹²CH₄ in this range are satisfactorily reproduced.     

High resolution measurements of the line positions and strengths of the 2ν2 band of H2CO

Spectra of the 2ν₂ band of formaldehyde have been obtained with high resolution (0.035 cm^?1). Measurements were made with path lengths of 8, 16, and 24 m and at sample pressures from 0.1 to 0.3 mm Hg at room temperature (～296°K). From these data, the following constants were determined for the 2ν₂ band in wavenumber units: v₀=3471.718±0.004,A=9.3958±030013,B=1.28100±0.00024,C=1.11662±0.00024, Tbbb=-12.8±0.5×10^-6,Taabb=60±5×10^-6. The line strengths were also obtained from the data. The strengths were analyzed to determine the band strength and the rotational factors. At 296°K, the strength of the 2ν₂ band was found to be 15.5 ± 0.9 cm^?1/(cm·atm).     

High-resolution vibration-rotation spectroscopy of fluoroform-d

The vibration-rotation spectrum of the ν₂ and ν₅ fundamentals of CDF₃ have been recorded using a Nicolet 7199 Fourier transform infrared spectrometer; in addition the Q branch and several subbands of each of these transitions have been investigated using a tunable semiconductor diode laser spectrometer. The Q branch and the K structure in several P(J) and R(J) subbands of ν₂, and in several Q branches of ν₅, are resolved and assigned for the first time. Constants derived for these bands are (in cm^?1) ν₂ = 1111.1823₆, B₂ = 0.32928₂, A₂ = 0.18872₂, α₂^B = 16.44₅ × 10^?4, α₂^B ? α₂^A = 12.43₅ × 10^?4, D₀^j = 3.7₃ × 10^?7, D₂^J = 4.8₃ × 10^?7; ν₅ = 975.39₁, B₅ = 0.33062, A₅ = 0.18887, α₅^B = 2.83₁ × 10^?4, α₅^A = 2.4₃ × 10^?4, ζ₅ = 0.736, D₅^J ? D₀^J = 1.2₂ × 10^?8. Some of these constants are nearly 100 times more precise than those reported in previous work.     

Infrared rotation-vibration spectra of ethane: The perpendicular band, ν7, of C2H6

The study of the gas-phase infrared spectrum of C₂H₆ in the region of the perpendicular CH-stretching band, ν₇, near 3000 cm^?1 is extended for the ΔK = + 1 subbands as far as K = 20. The spectral resolution of ～0.030 cm^?1 is increased to ～0.015 cm^?1 by deconvolution. The earlier investigation of this band for KΔK = +9 to ?5, is repeated with greater accuracy, providing more reliable ground-state constants (cm^?1): B₀ = 0.663089 ± 24, D₀^J = (0.108 ± 4) × 10^?5, D₀^JK = (0.50 ± 7) × 10^?5. The molecular constants (cm^?1) for the ν₇ fundamental are B₇ = 0.66310 ± 3, A₇ = 2.682, ν₀ = 2985.39, ζ₇ = 0.128. A discussion of resonance effects in this band, in particular x-y-Coriolis and Fermi resonance, is given.     

Measurement of the rate of ν e+d → p+p+e − interactions produced by 8B solar neutrinos at the Sudbury Neutrino Observatory

Solar neutrinos from the decay of ⁸B have been detected at the Sudbury Neutrino Observatory (SNO) via the charged current (CC) reaction on deuterium and by the elastic scattering (ES) of electrons. The CC reaction is sensitive exclusively to ν _e, while the ES reaction also has a small sensitivity to ν _μ and ν _τ. The flux of ν _e from ⁸B decay measured by the CC reaction rate is φ ^CC(ν _e )=[1.75±0.07(stat.) _?0.11 ^+0.12 (syst.)×0.05(theor.)]×10⁶cm^?2s^?1. Assuming no flavor transformation, the flux inferred from the ES reaction rate is φ ^ES(ν _x )=[2.39±0.34(stat.) _?0.14 ^+0.16 (syst.)]×10⁶cm^?2s^?1. Comparison of φ ^CC(ν _e) to the Super-Kamiokande collaboration’s precision value of φ ^ES(ν _x) yields a 3.3σ difference, assuming the systematic uncertainties are normally distributed, providing evidence that there is a nonelectron flavor active neutrino component in the solar flux. The total flux of active ⁸B neutrinos is thus determined to be (5.44±0.99)×10⁶ cm^?2 s^?1, in close agreement with the predictions of solar models.     

Vibration-rotation spectra of ethane and deuteroethanes: The ν2 band of CH3CD3

The ν₂ band of CH₃CD₃ has been measured under an effective resolution of 0.04 cm^?1. About 400 transitions observed in the region from 2130 to 2060 cm^?1 have been identified as due to the ν₂ fundamental band. The least-squares analysis of these transitions yields the band constants: ν₀ = 2089.957, B′ = 0.548937, D_J′ = 6.97 × 10^?7, D_JK′ = 1.92 × 10^?6, A′ - A″ = ?0.01158, and D_K′ - D_K″ = 1.30 × 10^?6 cm^?1. The ground-state constants B″, D_J″, and D_JK″ are fixed to the values obtained from microwave spectroscopy.     

Analysis of the ν6(A″2) band of cyclopropane-d6 recorded under high resolution

The parallel band ν₆(A″₂) of C₃D₆ near 2336 cm^?1 has been studied with high resolution (Δν = 0.020 – 0.024 cm^?1) in the infrared. The band has been analyzed using standard techniques and the following parameters have been determined: B″ = 0.461388(20) cm^?1, D″_J = 3.83(17) × 10^?7 cm^?1, ν₀ = 2336.764(2) cm^?1, α^B = (B″ ? B′) = 8.823(12) × 10^?4 cm^?1, β^J = (D″_J ? D′_J) = 0, and α^C = (C″ ? C′) = 4.5(5) × 10^?4 cm^?1.     

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.     

Analysis of the ν1 band of CH3I

The rotational structure of the infrared band ν₁ of CH₃I has been studied at a resolution of 0.04 cm^?1 using a grating spectrometer. In the analysis including 470 lines a resonance, explained to be caused by ν₂ + 2ν₆^±2, has been taken into account. The molecular constants derived include, e.g., α₁^A = 0.051129(14) cm^?1 and α₁^B = 0.0983(9) × 10^?3 cm^?1.     

Measurement and analysis of the infrared absorption spectrum of the 2ν2 band of 12CH4

Approximately 500 infrared absorption lines with room-temperature strengths between 3 × 10^?5 and 1 × 10^?2 atm^?1 were assigned to the 2ν₂ band of ¹²CH₄ in the region from 2930 to 3250 cm^?1. These determine 207 of the 212 upper-state energy levels through J′ = 12 as well as a number of levels with J′ = 13 and 14. All but 17 of the levels with J′ ≤ 12 are calculated to 0.03 cm^?1 or better on the basis of a Hamiltonion that contains Coriolis and Fermi interaction terms coupling the upper states of the five bands, 2ν₄, ν₂ + ν₄, ν₁, ν₃, and 2ν₂.