Double-quantum NMR spectroscopy of P species submitted to very large CSAs

We introduce an original pulse sequence, , which is a block super-cycled sequence employing as basic element a π pulse sandwiched by ‘window’ intervals. This homonuclear dipolar recoupling method allows the efficient excitation of double-quantum coherences between spin-1/2 nuclei submitted to very large chemical shift anisotropy. We demonstrate that this technique can be employed in double-quantum ↔ single-quantum ³¹P homonuclear correlation experiment at high magnetic field (B₀  14 T) and high MAS frequencies (ν_R  30 kHz). The performances of are compared to those of the double-quantum recoupling methods, such as BABA and bracketed fp-RFDR, which were already employed at fast MAS rates. The sequence displays a higher robustness to CSA and offset than the other existing techniques.     

High-resolution infrared and theoretical study of four fundamental bands of gaseous 1,3,4-oxadiazole between 800 and 1600 cm

The Fourier transform infrared spectrum of gaseous 1,3,4-oxadiazole, C₂H₂N₂O, has been recorded in the 800–1600 cm⁻¹ wavenumber region with a resolution around 0.0030 cm⁻¹. The four fundamental bands ν₉(B₁; 852.5 cm⁻¹), ν₁₄(B₂; 1078.5 cm⁻¹), ν₄(A₁; 1092.6 cm⁻¹), and ν₂(A₁; 1534.9 cm⁻¹) are analyzed by the standard Watson model. Ground state rotational and quartic centrifugal distortion constants are obtained from a simultaneous fit of ground state combination differences from three of these bands and previous microwave transitions. Upper state spectroscopic constants are obtained for all four bands from single band fits using the Watson model. The ν₄ and ν₁₄ bands form a c-Coriolis interacting dyad, and the two bands are analyzed simultaneously by a model including first and second order Coriolis resonance using the ab initio predicted Coriolis coupling constant . An extended local resonance in ν₂ is explained as higher order b-Coriolis type resonance with ν₆ + ν₁₀, which is further perturbed globally by the ν₁₅ + ν₁₀ level. A fit of selected low-J transitions to a triad model including ν₂(A₁), ν₆ + ν₁₀(B₁), and ν₁₅ + ν₁₀(A₂) using an ab initio calculated Coriolis coupling constant is performed.The rotational constants, ground state quartic centrifugal distortion constants, anharmonic frequencies, and vibration–rotational constants (α-constants) predicted by quantum chemical calculations using a cc-pVTZ and TZ2P basis with B3LYP methodology, are compared with the present experimental data, where there is generally good agreement. A complete set of anharmonic frequencies and α-constants for all fundamental levels of the molecule is given.     

On the high resolution spectroscopy and intramolecular potential function of SO2

Two weak stretching bands, ν₁ + 3ν₃ and 3ν₁ + ν₃, of the sulfur dioxide molecule have been recorded at high resolution and analyzed for the first time with using a Fourier transform Bruker IFS-120 HR interferometer. About 1000 transitions with J^max. = 51, , and 900 transitions with J^max. = 53, have been assigned to the bands ν₁ + 3ν₃ and 3ν₁ + ν₃, respectively. Analysis of the recorded spectra was made using the model of isolated vibrational states. Parameters obtained from the fit reproduce the initial experimental ro-vibrational energies with the rms deviation of 0.0006 and 0.0012 cm⁻¹ for the bands, 3ν₁ + ν₃ and ν₁ + 3ν₃, respectively. The problem of determination of the intramolecular potential function of SO₂ is discussed.     

: A quantitative measure of NMR signal receiving efficiency

Recognizing that the sensitivity of NMR is influenced by factors such as conductance and dielectric constant of the sample, we propose the receiving efficiency to characterize how efficiently the NMR signal can be observed from a unit transverse magnetization in a sample under optimal probe tuning and matching conditions. Conveniently, the relative receiving efficiency can be defined as the ratio of the NMR signal induced by a unit transverse magnetization in a sample of interest and a reference solution. Based on the reciprocal relationship between excitation and observation in NMR, the relative receiving efficiency can be correlated with the 90° pulse length (τ₉₀). In the special case of perfect probe tuning (impedance matched to 50 Ω), is inversely proportional to τ₉₀. Application of the NMR receiving efficiency in quantitative analysis potentially enables a single external concentration reference for almost any sample, eliminating the need to know its exact chemical composition or detailed electromagnetic properties.     

Resonant Auger decay study of core-excited OCS

The present work aims at characterizing short-lived C1s⁽⁻¹⁾π^*(1) core-excited states of the OCS molecule based on the analysis of the vibrational fine structure and lineshape profiles of the high-resolution resonant Auger decay spectra recorded at the excitation energies along the C1s→π^* resonance in the binding energy region 15–19 eV. Very different behavior in terms of lineshape and resonant enhancement is observed for the , and final states. This is explained by (1) the variation in the C–O bond lengths for the states involved in the electronic relaxation and (2) different contributions in terms of Mulliken population to the molecular orbitals determining the electronic character of the corresponding states. Since the final-state geometries are known from a number of previous experiments and ab initio calculations, the geometry of the C1s⁽⁻¹⁾π^*(1) intermediate states can be predicted in analogy with e.g. the N₂, CO₂ and N₂O molecules.     

High resolution FTIR spectroscopy of pentafluoroethane: perturbations in the Coriolis doublet of ν4 and ν13

The FTIR spectrum of pentafluoroethane (R125) was measured in the mid infrared region from 900 to 4000 cm⁻¹. Vibrational assignments for R125 are revised by comparison of previous and current experimental data with ab initio calculations at both the MP2/6-311+(d,p) and B3LYP/TZV+(3df,3p) levels of theory. High resolution FTIR spectra were recorded at room temperature and in an enclosive flow cell at a rotational temperature of 140 K. The cold spectrum was sufficiently resolved to enable rovibrational analyses of the overlapping ν₄ (1200.7341 cm⁻¹) and ν₁₃ (1223.3 cm⁻¹) bands, which have a/c hybrid and b-type character, respectively. Ground state combination differences were used to confirm assignment of 2375 lines to ν₄ (J_max = 86, K_{a max} = 50) and 2921 lines to ν₁₃ (J_max = 60, K_{a max} = 54). Effective rotational and centrifugal distortion constants were determined for ν₄, and the polarization ratio was found to be . Severe Coriolis perturbations prevent any satisfactory fit to the ν₁₃ band.     

Double-quantum homonuclear NMR correlation spectroscopy of quadrupolar nuclei subjected to magic-angle spinning and high magnetic field

We present a new application of the symmetry-based dipolar recoupling scheme, for exciting directly double-quantum (2Q) coherences between the central transition of homonuclear half-integer quadrupolar nuclei. With respect to previously published 2Q-recoupling methods (M. Eden, D. Zhou, J. Yu, Chem. Phys. Lett. 431 (2006) 397), the sequence is used without π/2 bracketing pulses and with an original super-cycling. This leads to an improved efficiency (a factor of two for spin-5/2) and to a much higher robustness to radio-frequency field inhomogeneity and resonance offset. The 2Q-coherence excitation performances are demonstrated experimentally by ²⁷Al NMR experiments on the aluminophosphates berlinite, VPI5, AlPO₄-14, and AlPO₄-CJ3. The two-dimensional 2Q–1Q correlation experiments incorporating these recoupling sequences allow the observation of 2Q cross-peaks between central transitions, even at high magnetic field where the difference in offset between octahedral and tetrahedral ²⁷Al sites exceeds 10 kHz.     

Electric field controlled g-factor in parabolic well determined by transport measurements

The Shubnikov de Haas oscillations in parabolic well are studied in the tilted magnetic field. The electric field displaces the electron wave function along Z-axis and leads to the strong variation of the average bare g-factor in such system. From the measurements of the filling factor ν_c at which the spin gap collapse occurs, we deduce the total Zeeman energy, which consists of the bare Zeeman energy and exchange-correlation term. By investigating of the variation of ν_c in tilted field we reliably extract the bare g-factor as a function of the gate voltage.     

Structural and electronic behavior of Sr2GdRuO6 complex perovskite

We report experimental and theoretical study of crystallographic lattice and electronic structure of Sr₂GdRuO₆ complex perovskite, which is used as precursor in the fabrication process of superconducting ruthenocuprate RuSr₂GdCu₂O₈. Samples were produced by the standard solid state reaction. Rietveld refinement of experimental X-ray diffraction patterns shows that material crystallizes in a monoclinic structure, which belongs to the P2₁/n (#14) space group, with lattice parameters , , , and tilt angle β=90.258. Calculations of electronic structure were performed by the density functional theory. The exchange and correlation potentials were included through the LDA+U approximation. Density of states (DOS) study was carried out considering the two spin polarizations. Results show Gd are majority responsible for the magnetic character in this material, but Ru contribution is also relevant because d-orbital is closer to Fermi level. Theoretical results evidence that Sr₂GdRuO₆ material behaves as a magnetic semiconductor, with 20μ_B effective magnetic moment.     

High-resolution FTIR spectroscopy of HNSO—Analysis of the highly perturbed ν4, ν6 and 2ν5 bands

We report a rovibrational analysis of the ν₄ and ν₆ fundamentals and the 2ν₅ overtone of HNSO from high-resolution Fourier transform infrared spectra. The ν₆ band (out-of-plane bend) centred at 757.5 cm⁻¹ is c-type. The ν₄ band (HNS bend) centred at 905.9 cm⁻¹ is predominantly a-type with a very weak b-type component (). Numerous global perturbations and localized avoided crossings affecting the v₄ = 1 rotational levels were successfully treated by inclusion of Fermi and c-axis Coriolis resonance terms between v₄ = 1 and v₅ = 2, and a b-axis Coriolis resonance term between v₄ = 1 and v₆ = 1. The latter term gives rise to an avoided crossing with an extraordinary ΔK_a = 5 selection rule. The Fermi resonance between v₄ = 1 and v₅ = 2 gives rise to strong mixing of their rotational wavefunctions in the vicinity of K_a = 18. The resultant borrowing of intensity made it possible for 2ν₅ transitions in the range K_a = 16–19 to be assigned and included in a global rovibrational treatment of all three band systems.     

The observation of hot bands in the 288 nm system of the FeCl2 radical

The 288 nm band system of FeCl₂ has been recorded with a sample produced in a warmed, free-jet expansion at moderately high resolution (with a linewidth of 0.28 cm⁻¹). Under these conditions, several hot bands are observed involving excitation of the symmetric and anti-symmetric stretching vibrations. The wavenumbers determined as a result for FeCl₂ in its ground ⁵Δ_g,4 state are and . No hot, sequence bands in the bending vibration were observed. The most likely explanation is that the wavenumber for ν₂ is essentially the same in both the electronic states involved (88 cm⁻¹). Additional strong hot bands are observed that are unrelated to the previously assigned electronic transitions; they appear to emanate from a low-lying electronic state of FeCl₂.     

Phase transitions in the quantum Hall liquid in a quantum wire

Two scenarios for the collapse of the ν=1 quantum Hall liquid (QHL) state, with the effective quantum wire (QW) width defined by the Fermi vector k_F, are studied. Here, ν for the QW is defined as the filling factor of Landau levels (LL) at the center of the QW. In the first one there is no electron redistribution at critical magnetic field , where the Fermi energy, E_F, coincides with the bottom of the empty upper spin-split LL. For the ν=1 state is unstable due to exchange-correlation effects and lateral confinement. In the second scenario, a transition to the ν=2 state occurs, with much smaller width, at . The latter scenario is analyzed in the Hartree–Fock approximation (HFA). Here the Hartree contribution to the total energy affects drastically due to strong electron redistribution in the QW. In both scenarios, the exchange-enhanced g-factor is suppressed at B_cr. The critical fields, activation energy, and optical g-factor obtained in the first scenario are very close to the measured ones.     

Effect of In-content on the optical properties of a-Se films

The optical transmission spectra of amorphous (a-) Se_1−xIn_x films, with x = 0.0, 0.05, 0.18 and 0.35, that prepared by thermal evaporation from their corresponding bulk ingots, are recorded over the spectral region of 500–2500 nm. A simple straight forward procedure proposed by Swanepeol has been applied to determine the two components of the complex refractive index (). The dispersion of is examined in terms of the Wemple and DiDomenico model and is discussed in terms of In-content. An estimation of various optical parameters such as, the optical energy gap (E_g = 1.96–1.33 eV), single oscillator energy (E_o = 3.95–3.16 eV), oscillator dispersion energy (E_d = 22.6–31.6 eV), lattice oscillator strength (E_l = 0.38–0.61 eV) and wavelength at zero material dispersion (λ_c = 2.0569–2.0879 μm) have been given and discussed in relation to the coordination number, hydrostatic density and formed chemical bonds that are introduced in the network of a-Se with the introduction of up to 35 at.% In.     

Observation of γ-delayed 3α breakup of the 15.11 and 12.71 MeV states in C

The reactions at 4.9 MeV and at 8.5 MeV have been used to investigate the γ decay of states in ¹²C. By measuring the four-body final state in complete kinematics we are able to detect γ transitions indirectly. We find γ transitions from the 15.11 MeV state in ¹²C to the 12.71, 11.83, 10.3 and 7.65 MeV states followed by their breakup into three α particles. The relative γ-ray branching ratios obtained are (1.2±0.3), (0.32±0.12), (1.4±0.2) and (4.4±0.8)%, respectively, with the remaining (92.7±1.0)% of the γ decays going to the bound states. We obtain Γ_α/Γ=(2.8±1.2)% for the isospin-forbidden α decay of the 15.11 MeV state. From the 12.71 MeV state we find γ transitions to the 10.3 and 7.65 MeV states. The relative γ-ray branching ratios are and , respectively, with the remaining of the γ decays going to the bound states. Finally, we discuss the relation between the β decay of ¹²N and ¹²B to states in ¹²C and the γ decay of the 15.11 MeV analog in ¹²C to the same states.     

Efficient heteronuclear dipolar decoupling in solid-state NMR using frequency-swept SPINAL sequences

Aiming to improve heteronuclear spin decoupling efficiency in NMR spectroscopy of solids and liquid crystals, we have modified the original Small Phase Incremental ALteration (SPINAL) sequence by incorporating a frequency sweep into it. For the resulting sequence, termed SW_f-SPINAL, the decoupling performance of a large number of sweep variants was explored by both numerical simulations and NMR experiments. It is found that introducing a frequency sweep generally increases both the ‘on-resonance’ decoupling performance and the robustness towards parameter offsets compared to the original SPINAL sequence. This validates the concept of extending the range of efficient decoupling by introducing frequency sweeps, which was recently suggested in the context of the frequency-swept SW_f-TPPM method. The sequence found to be best performing among the SW_f-SPINAL variants consists of fully swept 16 pulse pairs and is designated (32)-SPINAL-32. Its good decoupling performance for rigid spin systems is confirmed by numerical simulations and also experimentally, by evaluating the CH₂ resonance of a powder sample of l-tyrosine under MAS. For moderate MAS frequencies, the new sequence matches the decoupling achieved with SW_f-TPPM, and outperforms all other tested sequences, including TPPM and SPINAL-64. (32)-SPINAL-32 also shows excellent decoupling characteristics for liquid crystalline systems, as exemplified by experiments on the 5CB liquid crystal.     

Gate-controlled de Haas–van Alphen effect in an interacting two-dimensional electron system

We have measured the de Haas–van Alphen (dHvA) oscillations of a gated two-dimensional electron system formed in a modulation-doped AlGaAs/GaAs heterojunction by means of a novel and highly sensitive cantilever magnetometer. We achieve a sensitivity of at a magnetic field by detecting the deflection of the cantilever using a fiber optic interferometer. The dHvA oscillation at ν=1 yields a thermodynamic energy gap that scales linearly with the applied magnetic field for . The slope corresponds to an exchange enhanced g factor g^*=3.5±0.3 originating from electron–electron interaction in the spin-polarized state of the 2DES.     

Search for the rare decays , , and

Rare decay modes , J/ψ→D⁻π⁺+c.c., and are searched for using events collected with the BESII detector at the BEPC. No signal above background is observed. We present upper limits on the branching fractions of , B(J/ψ→D⁻π⁺)<7.5×10⁻⁵, and at the 90% confidence level.     

Structural and optical properties of nearly stress-free m-plane ZnO film on (1 0 0) γ-LiAlO2 with a GaN buffer layer by metal-organic chemical vapor deposition

m-plane ZnO film was epitaxially deposited on (1 0 0) γ-LiAlO₂ by metal-organic chemical vapor deposition at 600 °C with a GaN buffer layer. The epitaxial relationships between ZnO and GaN, GaN and (1 0 0) γ-LiAlO₂ were determined by X-ray diffraction Φ-scans. There exhibits very small decrease for the E₂ mode shift (0.3 cm⁻¹) of ZnO in the Raman spectrum, which indicates the epitaxial ZnO film was under a slight tensile stress (5.77 × 10⁷ Pa). Unlike the highly strained a-plane ZnO, temperature dependent photoluminescence spectra show that the free A exiton emission was observed with the temperature ≤138 K.     

Multiple resonance heteronuclear decoupling under MAS: dramatic increase of spectral resolution at moderate magnetic field and MAS frequencies

The effects of multiple-resonance heteronuclear decoupling under magic angle spinning (MAS) on the resolution of one-dimensional ¹⁹F and ³¹P and various two-dimensional MAS NMR spectra and on the residual non-refocusable coherence lifetimes in fluorinated aluminophosphate AlPO₄-CJ2, i.e. a compound that contains numerous highly abundant nuclei but no homonuclear spin bath, has been investigated. The design of the four-channel (¹H, ¹⁹F, ²⁷Al, ³¹P) MAS probe used for this study is first described. ¹H and ¹H–²⁷Al double-resonance decouplings allows lengthening the optimized transverse relaxation and increasing the resolution in the ¹⁹F and ³¹P dimensions. Under the application of multi-nuclear decoupling, a two-dimensional ¹⁹F–³¹P CP-HETCOR correlation spectrum for AlPO₄-CJ2 is recorded with unprecedented high-resolution in the two dimensions. Moreover, because ¹H-decoupling increases the ¹⁹F , it has been applied during the entire duration of the 2D NMR experiments, allowing the direct use of residual small interactions to generate ¹⁹F–¹⁹F and ¹⁹F–²⁷Al 2D NMR correlation spectra in AlPO₄-CJ2.     

Unfamiliar integrals and motions down the ‘plug-hole’ potential

The orbits in the potentials ψ=−CzR⁻²+ζ(R), (ζ arbitrary) have integrals E, and . Thus the z-velocity is proportional to the number of turns made around the axis! The Poisson Bracket [h,I] is not zero so Liouville’s integrability theorem does not apply. Starting from the self-similar potential with ζ∝R⁻¹, we find some orbits that spiral around cones and explore general orbits in this strange system.