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.     

Quantitative Evaluation of the Lactate Signal Loss and Its Spatial Dependence in PRESS Localized H NMR Spectroscopy

Localized ¹H NMR spectroscopy using the 90°−t₁−180°−t₁+t₂−180°−t₂−Acq. PRESS sequence can lead to a signal loss for the lactate doublet compared with signals from uncoupled nuclei which is dependent on the choice of t₁ and t₂. The most striking signal loss of up to 78% of the total signal occurs with the symmetrical PRESS sequence (t₁=t₂) at an echo time of 2/J (290 ms). Calculations have shown that this signal loss is related to the pulse angle distributions produced by the two refocusing pulses which leads to the creation of single quantum polarization transfer (PT) as well as to not directly observable states (NDOS) of the lactate AX₃ spin system: zero- and multiple-quantum coherences, and longitudinal spin orders. In addition, the chemical shift dependent voxel displacement (VOD) leads to further signal loss. By calculating the density operator for various of the echo times TE=n/J, n=1, 2, 3, …, we calculated quantitatively the contributions of these effects to the signal loss as well as their spatial distribution. A maximum signal loss of 75% can be expected from theory for the symmetrical PRESS sequence and TE=2/J for Hamming filtered sinc pulses, whereby 47% are due to the creation of NDOS and up to 28% arise from PT. Taking also the VOD effect into account (2 mT/m slice selection gradients, 20-mm slices) leads to 54% signal loss from NDOS and up to 24% from PT, leading to a maximum signal loss of 78%. Using RE-BURP pulses with their more rectangular pulse angle distributions reduces the maximum signal loss to 44%. Experiments at 1.5 T using a lactate solution demonstrated a maximum lactate signal loss for sinc pulses of 82% (52% NDOS, 30% PT) at TE=290 ms using the symmetrical PRESS sequence. The great signal loss and its spatial distribution is of importance for investigations using a symmetrical PRESS sequence at TE=2/J.     

Signal Enhancement Using 45° Water Flipback for 3D N-Edited ROESY and NOESY HMQC and HSQC

A novel implementation of the water flipback technique employing a 45° flip-angle water-selective pulse is presented. The use of this water flipback technique is shown to significantly enhance signal in 3D ¹⁵N-edited ROESY in a 20 kDa complex of the vnd/NK-2 homeodomain bound to DNA. The enhancement is seen relative to the same experiment using weak water presaturation during the recovery delay. This enhancement is observed for the signals from both labile and nonlabile protons. ROESY and NOESY pulse sequences with 45° water flipback are presented using both HMQC and HSQC for the ¹⁵N dimension. The 45° flipback pulse is followed by a gradient, a water selective 180° pulse, and another gradient to remove quadrature images and crosspeak phase distortion near the water frequency. Radiation damping of the water magnetization during the t₁ and t₂ evolution periods is suppressed using gradients. Water resonance planes from NOESY–HMQC and NOESY–HSQC spectra show that the HMQC version of the pulse sequences can provide stronger signal for very fast exchanging protons. The HSQC versions of the ROESY and NOESY pulse sequences are designed for the quantitative determination of protein–water crossrelaxation rates, with no water-selective pulses during the mixing time and with phase cycling and other measures for reducing axial artifacts in the water signal.     

Control of susceptibility-related image contrast by spin-lock techniques

Macroscopic magnetic field inhomogeneities might lead to image distortions, while microscopic field inhomogeneities, due to susceptibility changes in tissues, cause spin dephasing and decreasing T₂ relaxation time. The latter effects are especially observed in the trabecular bone and in regions adjacent to air-containing cavities when gradient-echo sequences are applied. In conventional MRI, these susceptibility-related signal voids can be avoided by applying spin-echo (SE) techniques. In this study, an alternative method for the examination and control of susceptibility-related effects by spin-lock (SL) radiofrequency pulses is presented: SL pulses were applied in two different susceptibility-sensitive sequence types: (a) between the jump and return 90° pulses in a 90°_x−τ−90°_−x magnetization-prepared Fast Low Angle Shot (FLASH) sequence and (b) between the 90° pulse and the 180° pulse in an asymmetric SE sequence. The range of Larmor frequencies used for spin locking can be determined for different B₁ amplitudes of the SL pulses, allowing control of image contrast by the amplitude of the SL pulses.     

Electrical conductivity of Ag/Na ion-exchanged titanosilicate glasses

The Ag₂O–TiO₂–SiO₂ glasses were prepared by Ag⁺/Na⁺ ion-exchange method from Na₂O–TiO₂–SiO₂ glasses at 380–450 °C below their glass transition temperatures (T_g), and their electrical conductivities were investigated as functions of TiO₂ content and the ion-exchange ratio (Ag/(Ag+Na)). In a series of glasses 20R₂O·xTiO₂·(80−x)SiO₂ with x=10, 20, 30 and 40 in mol%, the electrical conductivities at 200 °C of the fully ion-exchanged glasses of R=Ag were in the order of 10⁻⁵ or 10⁻⁴ S cm⁻¹ and were 1 or 2 orders of magnitude higher than those of the initial glasses of R=Na. The glass of x=30 exhibited the highest increase of conductivity from 3.8×10⁻⁷ to 1.3×10⁻⁴ S cm⁻¹ at 200 °C by Ag⁺/Na⁺ ion exchange among them. When the ion-exchange ratio was changed in 20R₂O·30TiO₂·50SiO₂ system, the electrical conductivity at 200 °C exhibited a minimum value of 7.6×10⁻⁸ S cm⁻¹ around Ag/(Ag+Na)=0.3 and increased steeply in the region of Ag/(Ag+Na)=0.5–1.0. When the ion-exchange temperature was changed from 450 to 400 °C, the conductivity of the ion-exchanged glass of x=30 decreased. The infrared spectroscopy measurement revealed that the ion-exchange temperature of 450 °C induced a structural change in the glass of x=30. The T_g of the fully ion-exchanged glass of x=30 was 498 °C. It was suggested that the incorporated silver ions changed the average coordination number of titanium ions to form higher ion-conducting pathway and resulted in high conductivity in the titanosilicate glasses.     

Inverse Laplace transforms of osculatory and hyperosculatory interpolation polynomials

In the numerical calculation of f(t), the inverse Laplace transform of F(p), where f(′) = (1/2πi) °_c−i∞^c+i∞ e^pt F(p)dp, sufficient accuracy is usually obtainable when p³F(p), s > 0, is replaced by an interpolating polynomial in 1/p. From the values of F(p) with F′(p), or with F′(p) and F″(p), for p at points equally spaced on the real axis, an osculatory or hyperosculatory interpolation polynomial for p⁸F(p), namely L_2n−1(x) or L_3n−1(x), where x = 1/p, is obtained in barycentric form. Then f(t) is calculated by a Gaussian-type quadrature formula employing complex values of L_2n−1 or L_3n−1 and instead of p^sF(p) which may be unknown or more difficult to compute. For calculating L_2n−1 and L_3n−1, auxiliary coefficients, suitable for economical storage in the program, are given exactly for n = 2(1)11 and n = 2(1)7, furnishing up to 21st and 20th degree accuracy, respectively.     

Interaction of oxovanadium(IV) with carboxylic ligands in aqueous solution: A thermodynamic and visible spectrophotometric study

The hydrolysis of VO²⁺ and the complex with sulfate were studied potentiometrically, spectrophotometrically and calorimetrically, in NaCl aqueous solution (0 < I ≤ 1 mol L^− 1) and at t = 25 °C. The formation of two hydrolytic species VO(OH)⁺ and VO₂(OH)₂²⁺ and one complex with sulfate was found, with log β = − 5.65 for the reaction VO²⁺ + H₂O = VO(OH)⁺ + H⁺, log β = − 7.02 for the reaction 2VO²⁺ + 2H₂O = (VO)₂(OH)₂²⁺ + 2H⁺ and log K = 1.73 for VOSO₄⁰ species (at I = 0.1 mol L^− 1 and t = 25 °C). For these species, using calorimetric data, ΔH and TΔS values were also obtained. By using the above values, interactions of VO²⁺ with acetate (ac), malonate (mal), succinate (suc), 1,2,3-propanetricarboxylate (tca) and 1,2,3,4-butanetetracarboxylate (btc) ligands were studied potentiometrically and spectrophotometrically. The formation of ML⁺, ML₂⁰ and MLOH⁰ for ac; ML⁰, MLH⁺, ML₂²⁻ and ML₂H⁻ for mal; ML⁰, MLH⁺ and MLOH⁻ for suc; ML⁻ and MLH⁰ for tca and ML²⁻, MLH⁻ and MLH₂⁰ for btc were found. Formation constants are reported at I = 0.1 mol L^− 1, together with SIT parameters for the dependence on ionic strength. By visible spectrophotometric measurements, λ_max and ε_max values for the relevant species in solution were determined.     

Study of in flight

An analysis of data on is presented at beam momenta 600 to 1940 MeV/c. There is evidence for an I=1, J^PC=2⁻⁺ resonance in ηηπ⁰ with mass M=1880±20 MeV and width 255±45 MeV, decaying strongly to a₂(1320)η; it is too strong to be explained as the high mass tail of π₂(1670)→a₂(1320)η. There is tentative evidence also for weak decays to f₀(1500)π. It makes a natural partner to the η₂(1860).     

Data storage characteristics of iron doped LiNbO3 under a 90° geometry two-beam coupling configuration

A 90° geometry two-beam coupling configuration was used to investigate the storage properties of 0.03 mol% iron-doped lithium niobate. Photographs of the real image and the subsequently stored images showed partial spatial fading. The maximum diffracted light intensity against recording time rapidly increased, reaching a maximum before gradually decaying. Decay time constants against recording time, t_rec varied in the same way as the diffracted intensity. Both plots reached a maximum at the same recording time of 3 min (I≈0.8 W cm⁻²) and 12 min (I≈0.4 W cm⁻²). Erasure decay times were found to vary with recording time; the best value found in this work was 8.5 min. Erasure curves all displayed an initial oscillatory nature, which may result from oscillation of the diffraction grating via a slow damped oscillation of the constituent electrons.     

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.     

Contribution to the Analysis of theA2←XA1“Wulf” Transition of Ozone by High-Resolution Fourier Transform Spectrometry

The analysis of the rotational structure of the high-resolution Fourier transform 0⁰₀absorption spectrum of the³A₂←X¹A₁band system of the “Wulf” transition of the isotopomer¹⁶O₃of ozone is reported for the first time. With a near pure case (b) coupling model for the upper triplet state, we have assigned a significant portion of the spectrum, mainly theF₁(J=N+ 1) andF₂(J=N) spin components, primarily in the lower frequency region of the band. The lines corresponding to theF₃(J=N− 1) component are weak at lower frequencies and heavily congested in the central and higher frequency regions of the spectrum. Perturbations and predissociation phenomena have reduced the effective lifetime of the metastable³A₂state and have also limited the number of transitions included in the least-squares fit of the band. Approximately 100 lines have been assigned in the range from 9100–9550 cm⁻¹. Three rotational, three centrifugal distortion, three spin–rotation, and one spin–spin constant were varied. The geometry of the molecule in the³A₂state, as determined from these constants, isr= 1.345 Å and θ = 98.9°, in good agreement withab initioresults.     

The Mechanism of Magnetically Tuned Singlet–Triplet Avoided Crossings in the ÃA2– A1 40 Band of Thioformaldehyde H2C=S

Magnetically tuned singlet–triplet perturbations in the 4¹Ã¹A₂–2¹3¹ã³A₂ system of thioformaldehyde, found in ortho-rotational states (I = 1, the two hydrogen spins parallel) have been identified as being caused by vibronic spin–orbit coupling. This perturbation mechanism has been confirmed in several avoided crossings observed in this work for para states (I = 0, hydrogen spins antiparallel) which are much stronger. Parametrization of the theory has led to a quantitative understanding of the experimental frequency-field relations, and to an accurate prediction of the rovibrational energies of the triplet state. This in turn permitted the detection of about 100 Doppler-limited 2¹3¹ã³A₂–0^{0 1}A₁ rovibronic transitions which led into fine structure states. The combined data was then used to determine a set of rotational, fine, and hyperfine triplet-state parameters, the term value T₀(2¹3¹ã³A₂) = (16 685.385 ± 0.002) cm⁻¹, and the spin–orbit vibronic singlet–triplet coupling constant, W_ST = (0.0691 ± 0.0016) cm⁻¹. A large number of frequency perturbations observed in the crossings, ranging from 2 to 300 MHz, can be explained with this single parameter.     

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.     

High-resolution infrared spectra of HCF3 in the ν6 (500 cm) and 2ν6 (1000 cm) regions: rovibrational analysis and accurate determination of the ground state constants C0 and DK

The high-resolution infrared spectrum of HCF₃ was studied in the ν₆ fundamental (near 500 cm⁻¹) and in the 2ν₆ overtones (near 1000 cm⁻¹) regions. The present study reports on the analysis of the hot bands in the ν₆ region, as well as the first observation and assignment of the 2ν₆² perpendicular band. Using ν₆, 2ν₆^±2–ν₆^±1 and 2ν₆² experimental wavenumbers, accurate coefficients C₀ and D_K⁰ of the K-dependent ground-state energy terms were obtained, using the so-called “loop method.” Ground-state energy differences Δ(K,J)=E₀(K,J)−E₀(K−3,J) were obtained for K=3–30. A least-squares fit of 81 such differences gave the following results (in cm⁻¹): C₀=0.1892550(15); D_K⁰=2.779(26) × 10⁻⁷.     

Looking for double beta decay of Nd to excited states of Sm by gamma ray spectroscopy

We have measured the gamma ray activity of a sample of 6189 grams of metallic Neodimium with a germanium detector. From the gamma energy spectrum recorded during almost 6500 hours we extract lower limits for the halflife of the inclusive (0ν + 2ν) ββ decay of ¹⁵⁰Nd to the first excited states of ¹⁵⁰Sm : t_1/2(0⁺ → 0₁⁺ > 1.0·10²⁰, t_1/2(O⁺ → 0₂⁺) > 2.0 · 10²⁾, t_1/2(0⁺ → 2₁⁺) > 9.1 · 10¹⁹.     

Dipolar Coupling Information in Multispin Systems: Application of a Compensated REDOR NMR Approach to Inorganic Phosphates

Anexperimental strategy has been developed for measuring multiple dipole–dipole interactions in inorganic compounds using the technique of rotational echo double resonance (REDOR) NMR. Geometry-independent information about the dipole couplings between the observe nuclear species S (arbitrary quantum number) and the heteronuclear species I (spin- ) can be conveniently obtained from the experimental curve of ΔS/S₀ versus dipolar evolution time by limiting the analysis to the initial data range 0 < ΔS/S₀ < 0.30. Numerical simulations have been carried out on a three-spin system of type SI₂ in order to assess the effect of the I–I homonuclear dipole–dipole coupling and the influence of experimental imperfections such as finite pulse length and misadjustments of the 180° pulses applied to the I-spin species. The simulations show further that within the initial data range the effects of such misadjustments can be internally compensated by a modified sequence having an additional 180° pulse on the I channel in the middle of the dipolar evolution periods. Experimental ²⁷Al{³¹P} REDOR results on the multispin systems Al(PO₃)₃, AlPO₄, [AlPO₄]₁₂(C₃H₇)₄NF, and Na₃PO₄ confirm the general utility of this approach. Thus, for applications to unknown systems the compensation strategy obviates calibration procedures with model compounds.     

Millimeter-Wave Spectroscopy, High-Resolution Infrared Spectrum, ab Initio Calculations, and Molecular Geometry of FPS

The transient thiophosphenous fluoride FPS was produced by pyrolysis of 2.5% F₂PSPF₂ in Ar at 1300–1800°C. High-resolution (≥0.004 cm⁻¹) Fourier transform infrared spectra of the a-type ν₁ and b-type ν₂ bands, centered respectively at 803.249 and 726.268 cm⁻¹, were measured and fitted to rotational and quartic centrifugal distortion parameters. The millimeter-wave spectrum, essentially b-type, was measured between 300 and 370 GHz in the ground state and in the ν₃ excited state for FP³²S and in the ground state for FP³⁴S. The frequencies were fitted to a Watson-type A-reduced Hamiltonian up to sextic distortion terms. High level ab initio calculations with large basis sets were performed on FPS and supported the first identification of its infrared and millimeter wave spectra. The calculated anharmonic force field provided precise ab initio rovibrational α constants which were combined with the experimental molecular parameters to determine an accurate equilibrium structure of the molecule: r_e(PS)=188.86 pm, r_e(PF)=158.70 pm, θ(FPS)=109.28°. The collision-controlled 1/e lifetime measured in a 10-Pa (1 : 20) F₂PSPF₂/Ar mixture was 2 s, more than two orders of magnitude larger than that of FPO under the same experimental conditions.     

Doppler-limited dye laser excitation spectroscopy of DCF

The dye laser excitation spectrum of the vibronic transition of DCF was observed between 17 200 and 17 400 cm⁻¹ with the Doppler-limited resolution. DCF was produced by the reaction of microwave-discharged CF₄ with CD₃F. The observed spectra, which were found to be nearly free of perturbations, were assigned to 858 transitions of the K′_a − K″_a = 4−5, 3−4, 2−3, 1−2, 0−1, 1−0, 2−1, 3−2, 3−3, 2−2, 1−1, 0−0, 2−0, and 0−2 subbands, and were analyzed to determine the rotational constants and centrifugal distortion constants for both the and à states. The rotational constants of DCF thus determined were combined with those of HCF to calculate the structural parameters for this molecule: r(C---H) = 1.138 Å, r(C---F) = 1.305 Å, and HCF = 104.1° for the ground state, and r(C---H) = 1.063 Å, r(C---F) = 1.308 Å, and HCF = 123.8° for the excited à state.     

Study of the pion trajectory in the photoproduction of leading neutrons at HERA

Energetic neutrons produced in ep collisions at HERA have been studied with the ZEUS detector in the photoproduction regime at a mean photon–proton center-of-mass energy of 220 GeV. The neutrons carry a large fraction 0.64<x_L<0.925 of the incoming proton energy, and the four-momentum transfer squared at the proton–neutron vertex is small, |t|<0.425 GeV². The x_L distribution of the neutrons is measured in bins of t. The (1−x_L) distributions in the t bins studied satisfy a power law dN/dx_L∝(1−x_L)^a(t), with the powers a(t) following a linear function of t: . This result is consistent with the expectations of pion-exchange models, in which the incoming proton fluctuates to a neutron–pion state, and the electron interacts with the pion.     

On integrability of generalized Veronese curves of distributions

Given a 1-parameter family of 1-forms γ(t) = γ₀+tγ₁+ ···+tⁿψ_n, consider the condition dγ(t)γ(t) = 0 (of integrability for the annihilated by γ(t) distribution w(t)). We prove that in order that this condition is satisfied for any t it is sufficient that it is satisfied for N = n + 3 different values of t (the corresponding implication for N = 2n + 1 is obvious). In fact we give a stronger result dealing with distributions of higher codimension. This result is related to the so-called Veronese webs and can be applied in the theory of bihamiltonian structures.