Rotational absorption spectrum of methylene fluoride in the 20–100 cm region

The pure rotational spectrum of CH₂F₂ was recorded in the 20–100 cm⁻¹ spectral range and analyzed to obtain rotation and centrifugal distortion constants. Analysis of the data yielded rotation constants: A = 1.6392173 ± 0.0000015, B = 0.3537342 ± 0.00000033, C = 0.3085387 ± 0.00000027, τ_aaaa = −(7.64 ± 0.46) × 10⁻⁵, τ_bbbb = −(2.076 ± 0.016) × 10⁻⁶, τ_cccc = −(9.29 ± 0.12) × 10⁻⁷, T₁ = (4.89 ± 0.20) × 10⁻⁶, and T₂ = −(1.281 ± 0.016) × 10⁻⁶cm⁻¹.     

Al satellite transition spectroscopy (SATRAS) of polycrystalline aluminium borate 9Al2O3 · 2B2O3

²⁷Al NMR spectra of polycrystalline aluminium borate 9Al₂O₃ · 2B₂O₃ have been measured at 104, 130 and 156 MHz. The parameters of the quadrupole interaction and the isotropic chemical shifts have been obtained by fitting the CT/MAS pattern and consideration of the inner satellite transitions m = 3/2 ↔ 1/2 and m = −1/2 ↔ −3/2. The gain in spectral resolution concerned with the observation of the MAS lines of the inner satellites leads to complete separation of the signals of AlO₆, AlO₅ and AlO₄ polyhedra. Also signals of structural groups of one and the same coordination number can be distinguished. Experimental and theoretical lineshape calculations are compared.     

Complete Determination of Nitrogen Quadrupole and Hyperfine Tensors in an Oxovanadium Complex by Simultaneous Fitting of Multifrequency ESEEM Powder Spectra

One-dimensional C- and X-band as well as two-dimensional X-band ESEEM experiments were performed on the complex oxobis(2-methylquinolin-8-olato) vanadium(IV) in frozen solution. A¹⁴N ESEEM simulation strategy based on initial first- and second-order perturbation analysis of peak positions in orientationally selected ESEEM spectra is presented. The constraint parameters extracted enable one to reduce the number of free fitting parameters for each nitrogen from 10 to 4. These are the α, β resp. the φ, θ Euler angles of the NQI and the HFI tensor defined in the coordinate system of the axialgtensor. The local symmetry of the complex allows one to reduce the number of free parameters to two angles only. Subsequently, a grid search in the remaining Euler space produced the starting parameters for the final fit of the¹⁴N hyperfine and quadrupole tensors. The anisotropic nitrogen hyperfine interaction tensor was found to be strongly nonaxial (0.06, 0.51, −0.57) MHz with the components significantly smaller than the isotropic hyperfine constant −6.18 MHz. In contrast, the quadrupole tensor withK= 0.58 MHz is close to axial (η = 0.13). These tensors share the principal axis normal to the ligand plane (as imposed by the local symmetry). The axes in the ligand plane are, however, rotated 50° with respect to each other. The orientation of the quadrupole tensor axes correlate within 10° with the orientation of the ligand plane following from the X-ray structure.     

Molecular structure, nuclear quadrupole coupling constant and dipole moment of nitrogen trichloride from microwave spectroscopy

The rotational constants of four isotopic species of nitrogen trichloride have been obtained from transitions in the millimeter region. Two r_s structures have been obtained with the following average values of the parameters. rN−C1=1.7535 ± 0.0020 A.The Stark effect of the J = 3 ← 2 transition was analyzed to obtaine the value 0.39 ± 0.01 D for the dipole moment of NCl₃. The measurement of the separation of the two strongest hyperfine components of the J = 2 ← 1 transition yielded the value of −108 ± 3 MHz for the N---Cl bond axis quadrupole coupling constant.     

Infrared and microwave spectra, molecular conformation and electric dipole moment of methyl thiolformate

The microwave spectrum (41-10 GHz) and the infrared spectrum (4000-50 cm⁻¹) of methyl thiolformate have been obtained and analyzed. The spectra are consistent with a single molecular conformation having a planar array of heavy atoms and with the alkyl group cis to the carbonyl group. The measured rotational constants are: A, 11042.22 MHz; B, 5118.27 MHz; C, 3562.03 MHz (κ = −0.5839). No internal rotation doublets were observed in the microwave spectrum for the ground vibrational state, which implies that the barrier hindering internal rotation of the methyl group is either much larger or much smaller than the corresponding value for methyl formate. If the former is true then a lower limit of 10.5 kJ mol⁻¹ may be placed on the barrier height.The dipole moment of methyl thiolformate was measured using the Stark effect to be 1.58 ± 0.05 Debyes (μ_A = 1.52 D; μ_B = 0.43 D) for the vapor, and for dilute solutions in benzene at 295 K the value of 1.6 ± 0.1 D was found from capacitance measurements.SCF computations using minimal basis sets of STO/3G atomic orbitals and extended basis sets of STO/4.31G atomic orbitals have been carried out for methyl thiolformate and methyl formate. Energy differences between rotational isomers and estimates of barrier heights are given together with the calculated dipole moments.     

Elementary reactions of formyl (HCO) radical studied by laser photolysis—transient absorption spectroscopy

Several elementary reactions of formyl radical of combustion importance were studied using pulsed laser photolysis coupled to transient UV–Vis absorption spectroscopy: HCO → H + CO (1), HCO + HCO → products (2), and HCO + CH₃ → products (3). One-pass UV absorption, multi-pass UV absorption as well as cavity ring-down spectroscopy in the red spectral region were used to monitor temporal profiles of HCO radical. Reaction (1) was studied over the buffer gas (He) pressure range 0.8–100 bar and the temperature range 498–769 K. Reactions (2a), (2b), (2c), (3a) and (3b) as well as the UV absorption spectrum of HCO, were studied at 298 and 588 K, and the buffer gas (He) pressure of 1 bar. Pulsed laser photolysis (308, 320, and 193 nm) of acetaldehyde, propionaldehyde, and acetone was used to prepare mixtures of free radicals. The second-order rate constant of reaction (1) obtained from the data at 1 bar is: k₁(He) = (0.8 ± 0.4) × 10⁻¹⁰exp(−(66.0 ± 3.4) kJ mol⁻¹/RT) cm³ molecule⁻¹ s⁻¹. The HCO dissociation rate constants measured in this work are lower than those reported in the previous direct work. The difference is a factor of 2.2 at the highest temperature of the experiments and a factor of 3.5 at the low end. The experimental data indicate pressure dependence of the rate constant of dissociation of formyl radical 1, which was attributed to the early pressure fall-off expected based on the theory of isolated resonances. The UV absorption spectrum of HCO was revised. The maximum absorption cross-section of HCO is (7.3 ± 1.2) × 10⁻¹⁸ cm² molecule⁻¹ at 230 nm (temperature independent within the experimental error). The measured rate constants for reactions (2a), (2b), (2c), (3a) and (3b) are: k₂ = (3.6 ± 0.8) × 10⁻¹¹ cm³ molecule⁻¹ s⁻¹ (298 K); k₃ = (9.3 ± 2.3) × 10⁻¹¹ cm³ molecule⁻¹ s⁻¹(298 and 588 K).     

Gamma-ray spectroscopy of Cr

A study of low-lying states in the self-conjugate nucleus ⁴⁸Cr has been performed with the reaction ⁴⁰Ca(¹⁰B, pnγ)⁴⁸Cr. Several techniques of γ-ray spectroscopy have been used: activity measurements, γ-ray angular distributions, γ-γ coincidences, p-n-γ triple coincidences, and recoil-distance lifetime measurements. The following level energies, spin-parity assignments, and lifetimes have been found: 752.4±0.5 keV, 2₁⁺, τ_m = 9.7±2.6 ps; 1858.7±0.7 keV, 4₁⁺, τ_m = 1.5_−0.5^+2.0 ps; 3532.7±1.2 keV, (6₁⁺); 4064.3±1.3 keV, ( 4), τ_m < 60 ps. The 2₁⁺ state in ⁴⁸Cr is found to have the lowest excitation energy and highest E2 transition strength (33±9 W.u.) among the 2₁⁺ states of even nuclei in the 1f shell.     

Observation of the π(1800) and (1880) mesons in decay

A partial-wave analysis of the reaction π⁻p→ηηπ⁻p at 18 GeV/c has been performed on a data sample of approximately 4000 events obtained by Brookhaven experiment E852. The J^PC=0⁻⁺π(1800) state is observed in the a₀(980)η and f₀(1500)π decay modes. It has a mass of 1876±18±16 MeV/c² and a width of 221±26±38 MeV/c². The J^PC=2⁻⁺π₂(1880) meson is observed decaying through a₂(1320)η. It has a mass of 1929±24±18 MeV/c² and a width of 323±87±43 MeV/c². Both states are potential candidates for non-exotic hybrid mesons.     

Line Intensities in the ν1, ν3, and 2ν2 Bands of H2Se

Using a high-resolution Fourier transform spectrum of hydrogen selenide in natural abundance, about 600 intensities of lines belonging to the ν₁, ν₃, and 2ν₂ bands of H₂⁸⁰Se were measured. A least-squares fit of these intensities was performed, allowing determination of the vibrational transition moments of these bands and their rotational corrections. Finally, the first derivatives of the dipole moment with respect to the normal coordinates q₁ and q₃ were found to be ∂μ_χ/∂q₁ = (−0.5938 ± 0.010) × 10⁻¹ and ∂μ_z/∂q₃ = (0.5683 ± 0.010) × 10⁻¹ Debye, respectively.     

The 2ν8 Band of CH3CN

The overtone band 2ν⁰₈ of CH₃CN around 720 cm⁻¹ has been measured on a Bruker Fourier transform spectrometer at a resolution of 0.003 cm⁻¹. Only the parallel band was observed, but due to the l(2, 2) resonance, ΔK = −2 lines leading to the v₈ = 2, l₈ = −2 levels with K = 1-3 could be seen. More information for the l₈ = ±2 component of the vibrational state v₈ = 2 was evaluated from the hot band 2ν^±2₈ - ν^±1₈. Altogether more than 1000 lines were assigned. In the fit pure rotational lines from literature were also combined. Among the results the anomalous A₀ - A′ values 4.6722(13) × 10⁻³ cm⁻¹ for the 2ν⁰₈ band and 7.0324(32) × 10⁻³ cm⁻¹ for the 2ν^±2₈ band are striking.     

KARMEN: Neutrino oscillation limits and new results with the upgrade

The neutrino experiment KARMEN is situated at the beam stop neutrino source ISIS which provides ν_μ's, ν_e's and from the π⁺−μ⁺-decay at rest. The oscillation channels ν_{μ → νe} and are investigated with a 56 t liquid scintillation calorimeter. No evidence for oscillations could be found with KARMEN, resulting in 90% CL exclusion limits of sin²(2Θ) < 8.5 · 10⁻³ ( ) and sin²(2Θ) < 4.0 · 10⁻² (ν_μ → ν_e) for Δm² > 100 eV². In 1996, the experiment has been upgraded by an additional veto counting system with a total coverage of 300 m². The new system allows the identification of cosmic muons in the vicinity of the detector. Vetoing these muons suppresses energetic neutrons from deep inelastic scattering of muons as well as from μ-capture by a factor of 40. Up to 1996, these neutrons represented the main background for oscillation search. The experimental sensitivity for will be significantly enhanced towards sin²(2Θ) 1.0 · 10⁻³ after a further measuring period of 2–3 years.     

Determination of the (Na) Sternheimer antishielding factor by Na NMR spectroscopy on sodium oxide chloride, Na3OCl

The (Na⁺) Sternheimer antishielding factor γ_∞ (Na⁺) was determined by ²³Na NMR spectroscopy on sodium oxide chloride, Na₃OCl. The quadrupolar coupling constant of the sodium ion in Na₃OCl was determined to QCC=11.34 MHz, which presents the largest coupling constant of a sodium nucleus observed so far. Applying a simple point charge model, the largest principal value of the electric field gradient at the sodium site was calculated to V_zz=−6.76762·10²⁰ V/m². From these values we calculated the (Na⁺) Sternheimer antishielding factor to γ_∞ (Na⁺)=−5.36. In sodium oxide, Na₂O, we observed an isotropic chemical shift of δ_CS=55.1 ppm, referenced to 1 M aqueous NaCl (δ=0 ppm).     

Microwave spectrum, structure, dipole moment, and internal rotation of fluoromethyl methyl ether

Microwave spectra of fluoromethyl methyl ether and its 10 isotopically substituted species were measured. The r_s structure of this molecule was determined from the observed moments of inertia. Structural parameters obtained for this molecule, which was in the gauche form, were compared with those of the analogous molecules. Dipole moments of the normal and two deuterated species were determined by Stark-effect measurements. For the normal species, the dipole moment is 1.744 ± 0.029 D making an angle of 100°54′ with the O---CH₂ bond toward the C---F direction and lies in the plane whose dihedral angles with the FCO and COC planes are 114°9′ and 44°56′, respectively. The barrier to internal rotation of the methyl group was calculated taking into account the coupling effect with the skeletal torsion using the observed splitting data of the spectra in the ground, first excited methyl torsional, and skeletal torsional states. The barrier, skeletal torsional frequency, and coupling term were determined to be V₃ = 1538 ± 40 cal/mole, ω_t = 158 ± 4 cm⁻¹, and V_s = 490 ± 500 cal/mole, respectively.     

The microwave spectrum of 1-phosphabut-3-ene-1-yne, CH2=CHCP

The new molecule 1-phosphabut-3-ene-1-yne, CH₂=CHCP, produced by pyrolyzing prop-1-ene-3-phosphorus dichloride, CH₂=CHCH₂PCl₂, was detected by microwave spectroscopy. The analysis of the rotational transitions indicates that the molecule is planar with constants: A₀ = 46 694(24), B₀ = 2807.7100(21), and C₀ = 2645.8356(21) MHz. These rotational constants indicate that the structure of the vinyl group is essentially the same as that in CH₂=CHCN and CH₂=CHCCH; r(C---C) = 1.432 Å and (C=C---C) = 123.9°. The dipole moment parameters are μ_A = 1.181(2), μ_B = 0.074(1), and μ = 1.183(2) D. The vibrational satellite spectra for the C---CP bending modes indicate that ν₁₁(a′) = 184 ± 30 cm⁻¹ and ν₁₅(a″) = 263 ± 30 cm⁻¹.     

Measurement of the mass of the Λb baryon

In a data sample of four million hadronic Z decays collected with the ALEPH detector at LEP, four Λ_b baryon candidates are exclusively reconstructed in the Λ_b → Λ_c⁺π⁻ channel, with the Λ_c⁺ decaying into pK⁻π⁺, , or Λπ⁺π⁺π⁻. The probability of the observed signal to be due to a background fluctuation is estimated to be 4.2 × 10⁻⁴. The mass of the Λ_b is measured to be 5614±21 (stat.) ± 4 (syst.) MeV/c².     

Status of the INR experiment on 2β decay of Cd

Measurements of ¹¹⁶Cd double beta decay with help of enriched¹¹⁶CdWO₄ crystal scintillator are in progress in the Solotvina Underground Laboratory. The last part of the exposition with the background rate less than 0.6 counts/y·kg·keV (in the region of interest 2.7–2.9 MeV) is about 19000 hours. The half-life limit T1/2(0ν)≥3.2·10²² y (90% C.L.) is obtained for neutrinoless 2β decay of ¹¹⁶Cd. It corresponds to restrictions on the values of the neutrino mass m_ν≤3.9 eV, right-handed admixtures in weak interaction η≤5.7·10⁻⁸, λ5.0·10⁻⁶ and R-parity violating parameter of minimal supersymmetric standard model ≤1.1·10⁻³. For neutrinoless modes with emission of one and two Majorons, the limits T1/2(0νM1)≥1.2·10²¹ y and T1/2(0νM2)≥2.4·10²⁰ y (90% C.L.) are determined. To advance these results to a level of the limit m_ν≤1–2 eV, the improved set-up with four enriched ¹¹⁶CdWO₄ crystals is in mounting low.     

Internal rotation in acetaldehyde

The microwave spectrum of acetaldehyde has been investigated in the frequency range from 7 to 40 GHz. A rather complete assignment of rotational transitions in the ground and torsionally excited states has been found with the help of microwave-microwave double resonance techniques. The spectral data have been analyzed using three different models for the overall and internal rotation problem including a nonrigid model. The threefold component of the internal rotation barrier was determined to be V₃ = 400 ± 2 cm⁻¹. The sixfold contribution V₆ = −10.9 ± 0.3 cm⁻¹ could only be adjusted reliably from data for both ground and torsionally excited states using the nonrigid model. The methods of barrier determinations have been critically reviewed. In an appendix, the Hamiltonian for a nonrigid model is derived based on structure relaxation of the methyl top during internal rotation.     

The Electric Dipole and the Nuclear Quadrupole Moment of Methyl Bromide in the Ground Vibrational State

A set of high-resolution Stark measurements at millimeter-wave frequencies is reported for CH₃⁷⁹Br and CH₃⁸¹Br. These results are analyzed together with previous data available in the literature to find new sets of molecular (rotational, hyperfine, and dipole moments) constants for both isotopic species. A particular improvement is obtained in the evaluation of the dipole moments, whose values are μ(79) = 1.82171 (26) 0, μ(8l) = 1.82185 (26) D, and for the hyperfine-structure parameters, which are estimated by assuming the most recent model for centrifugal distortion (M. R. Aliev and J. T. Hougen, J. Mol. Spectrosc.106, 110-123 (1984)), obtaining eqQ⁷⁹₀ = 577.1088 (57) MHz, χ⁷⁹_J = −0.63 (16) kHz, χ⁷⁹_K = 12.6 (16) kHz and eqQ⁸¹₀ = 482.1030 (94) MHz, χ⁸¹_J = −0.57 (17) kHz, χ⁸¹_K = 9.3 (22) kHz.     

High-resolution infrared and millimeterwave spectra of the v3=1 vibrational state of NF3 at 907 cm

The ν₃^±1 perpendicular band of ¹⁴NF₃ ( cm⁻¹) has been studied with a resolution of 2.5 × 10⁻³ cm⁻¹, and 3682 infrared (IR) transitions (J_max=55, K_max=45) have been assigned. These transitions were complemented by 183 millimeterwave (MMW) rotational lines (J_max=25, K_max=19) in the 150–550 GHz region (precision 50–100 kHz). The kl=+1 level reveals a strong A₁/A₂ splitting due to the l(2,2) rotational interaction (q=−4.05 × 10⁻³ cm⁻¹) while the kl=−2 and +4 levels exhibit small A₁/A₂ splittings due to l(2,−4) and l(0,6) rotational interactions. All these splittings were observed by both experimental methods. Assuming the v₃=1 vibrational state as isolated, a Hamiltonian model of interactions in the D reduction, with l(2,−1) rotational interaction (r=−1.96 × 10⁻⁴ cm⁻¹) added, accounted for the observations. A set of 26 molecular constants reproduced the IR observations with σ_IR=0.175 × 10⁻³ cm⁻¹ and the MMW data with σ_MMW=134 kHz. The Q reduction was also performed and found of comparable quality while the QD reduction behaved poorly. This may be explained by a predicted Coriolis interaction between v₃=1 and v₁=1 (A₁, 1032.001 cm⁻¹) which induces a slow convergence of the Hamiltonian in the QD reduction but has no major influence on the other reductions. The experimental equilibrium structure could be calculated as: r_e(N–F)=1.3676 Å and (FNF)=101.84°.     

Pyroelectric properties in three phases coexistence Pb[(Mn0.33Nb0.67)0.5(Mn0.33Sb0.67)0.5]0.08(ZrxTi1−x)0.92O3 lead ceramics

The bulk dense Pb[(Mn_0.33Nb_0.67)_0.5(Mn_0.33Sb_0.67)_0.5]_0.08(Zr_xTi_1−x)_0.92O₃ pyroelectric ceramics have been successfully prepared by the conventional solid method. The effect of three phases coexistence in the ceramics is studied. When x = 0.95 and 0.85 in the ceramics, the maximum pyroelectric coefficient peaks appear at 23 °C and 45 °C, and the maximum values are 26.5 × 10⁻⁴ C/m² °C and 25.5 × 10⁻⁴ C/m² °C, respectively. The maximum pyroelectric coefficient appears large while the peaks widths are small. When the two kinds of ceramic powders mixed with the mol ratio of 2:1, the pyroelectric coefficient of the ceramics is above 10.0 × 10⁻⁴ C/m² °C in a broad temperature range from 20 °C to 55 °C. The possible physical mechanism of the temperature broadened phenomenon is briefly discussed.