Comparison of the Effects of Different <Superscript>19</Superscript>F <Emphasis Type="Italic">π</Emphasis> Pulses on the Sensitivity and Phaseability of the <Superscript>19</Superscript>F-<Superscript>13</Superscript>C HSQC

The ¹⁹F-¹³C heteronuclear single quantum coherence (HSQC) experiment is vital for the structural elucidation of polyfluorinated organic species, yet its sensitivity and phaseability are limited by difficulties in uniform excitation of the widely disperse ¹⁹F spectral window. Adiabatic pulses of different types have previously been employed to generate effective π pulses for inversion and refocussing, but a systematic comparison of various adiabatic and other inversion pulses has not been published. In this work, it was observed that the use of a broadband inversion pulse (BIP) during the t ₁ evolution period resulted in properly phaseable spectra for experiments optimized to detect ¹ J _CF, in contrast to CHIRP or WURST adiabatic pulses. For the INEPT and reverse-INEPT transfer segments of the HSQC, optimal sensitivity for resonances distant from the transmitter frequency was afforded by optimized universal rotation (BURBOP) or CHIRP pulses. In HSQC experiments with delays optimized for two-bond correlations, only the use of BURBOP pulses in INEPT and reverse-INEPT sequences afforded spectra cleanly phaseable across the F ₂ and F ₁ spectral windows. This observation is supported by off-resonance pulsed field gradient spin-echo experiments.     

Complete Dipolar Decoupling ofC and Its Use in Two-Dimensional Double-Quantum Solid-State NMR for Determining Polymer Conformations

A multiple-pulse technique for complete dipolar decoupling of directly bonded¹³C-labeled sites is described. It achieves significant spectral simplifications in a recently introduced two-dimensional double-quantum solid-state NMR experiment for determining torsion angles. Both homonuclear and heteronuclear dipolar couplings are removed by combining a¹³C multiple-pulse sequence with continuous-wave irradiation on the protons. The¹³C sequence has a fundamental 10-pulse cycle which is a significantly modified magic-sandwich-echo sequence. The crucial heteronuclear decoupling is achieved by breaking the 360° “inner” pulses in the magic sandwich into 90° pulses and spacing them by¹H 360° pulse lengths. Spectral artifacts typical of multiple-pulse sequences are eliminated by phase shifts between cycles. In contrast to many other multiple-pulse decoupling sequences, the long window in the cycle is the dwell time and can be longer than the inverse dipolar coupling, which makes the sequence practical for direct detection even with long pulse ring-down times. A modification of the sequence to scale the chemical shift and increase the effective spectral width is also presented. The 1D and double-quantum 2D experiments are demonstrated on polyethylene with 4%¹³C–¹³C spin pairs. The potential of this approach for distinguishing segmental conformations is illustrated by spectral simulations of the two-dimensional ridge patterns that correlate double-quantum and single-quantum chemical-shift anisotropies.     

Spatial localization in the cyclicJ heteronuclear rotating frame coherence transfer

The theory of spatial localization for theJ heteronuclear rotating frame coherence transfer in the presence of the main magnetic field gradient is presented. The simplified case of an AX spin-1/2 pair in a liquid was considered. The two dimensional spatial profile for a cyclicJ heteronuclear rotating frame coherence transfer for¹H and¹³C pair was evaluated and the applications to localized heteronuclear spectroscopy and imaging are discussed.     

Offset Profiles of Selective Pulses in Isotopically Labeled Macromolecules

The experimental verification of offset profiles and calibration of selective pulses in NMR is usually carried out with doped water samples but not under conditions typical of macromolecules with shortT₂, longT₁, and possibly homo- and heteronuclear couplings. A new method for selective excitation in isotopically labeled macromolecules is shown to be particularly suited to this purpose. This is illustrated for a backbone amide resonance in a sample of¹⁵N-labeled human ubiquitin.     

Spatial localization in the heteronuclear coherence transfer from scalar order

The spatial localization of the heteronuclear coherence transfer from scalar order was analyzed for a rectangular and an adiabatic remagnetization contact pulses. The transferred coherence amplitudes with and without localization were evaluated for different experimental conditions and an AX-1/2 spin-pair system. The use of this method for¹³C localized spectroscopy is discussed.     

Heteronuclear Double-Quantum-Coherence Selection with Magnetic-Field Gradients in Diffusion Experiments

A 3.5-fold reduction in the magnitude of the magnetic-field-gradient pulses was achieved in a ³¹P NMR pulsed-field-gradient spin-echo experiment, used to measure the diffusion coefficient of a phosphorus-containing solute; this reduction involved a variant of a heteronuclear ′inverse-detection′ pulse sequence. The attendant eddy currents, set up in the conducting elements of the probe and magnet were reduced because of the smaller current required in the field-gradient coils. Linear magnetic-field gradients were also used in the pulse sequence to select heteronuclear double-quantum coherences, thus obviating the requirement for extensive phase cycling and potential dynamic range problems, because any signal that arose from magnetization that had not been double-quantum coherent was "spoiled" in the experiment prior to signal detection. The utility of the pulse sequence and the necessary modifications to the standard Stejskal and Tanner analysis that are required for data from the experiment are illustrated with the heteronuclear-coupled, ¹H-³¹P, system of neutralized phosphorus acid [HPO(OH)₂] in water.     

Saturation of the acoustic waves produced by pulsed arcs

Rapid simultaneous measurements of the arc current and voltage and the emitted acoustic wave were made on a small 20 A DC arc in open air, which was subjected to current pulses ranging in amplitude from 0·4 kA to 40 kA and in rise time from 10^?4 s to 10^?7 s. The results show that for a rise time Δt < 10^?5s, the amplitude of the pressure wave generated by the arc no longer varies with Δt but remains constant for a given amplitude of the current pulse. An additional study shows that this saturation is accompanied by a modification in the electrical behaviour of the arc, which suggests that the observed saturation is due to the arc itself and not to absorption of the pressure wave in the surrounding air.     

The effect of mechanical relaxation on ultra-fast charge pulses in flexible epoxy resin nanocomposites

Previously we have reported the existence of small-amplitude charge pulses in crosslinked Polyethylene (XLPE) and epoxy resin with a mobility several orders of magnitude higher than that found for the incoherent charge transport relevant to the steady state current. Here the relationship of this phenomenon to mechanical relaxation in the material is investigated by using a series of epoxy resin nanocomposites based on a resin that has its flexibility increased above that of the fully cured glassy epoxy network by the addition of a suitable flexibilizing chemical. Differential Scanning Calorimetry (DSC) measurements show that the stiffness of the nanocomposite is progressively increased as the nanoparticle concentration increases. Pulsed Electro-Acoustic (PEA) measurements reveal that both positive and negative fast charge pulses exist in the unfilled epoxy at 45 and 70°C under a field of 10?kV/mm with mobility 5×10^?10 to 9×10^?10 m²?V^?1?s^?1, amplitude between 2×10^?5 and 3.6×10^?5 C?m^?2 and repetition rates between 8 and 12?s^?1. These values are reduced progressively as the nanoparticle concentration is increased from 0% in the unfilled epoxy. A???-mode mechanical relaxation is identified in the loss modulus by Dynamical Mechanical Analysis (DMA), whose activation energy moves to higher values with increasing nanoparticle concentration. It is shown that the repetition rates of both positive and negative pulses have similar values and are correlated with the ??-mode activation energy; a similar correlation is found for the activation energy of the mobility of positive pulses. The correlation of the activation energy of the mobility of negative pulses and that of the ??-mode is weaker although both show a progressive increase with nanoparticle concentration. The modification of the fast charge pulse properties by the mechanical stiffness of the epoxy nanocomposite is discussed in terms of the theory presented previously for their formation and transport.     

Femtosecond pulsed laser deposition of diamond-like carbon films: The effect of double laser pulses

The bonding structure of carbon films prepared by pulsed laser deposition is determined by the plasma properties especially the change of the kinetic energy. Using double laser pulses the ablation process and the characteristics of the generated plasma can be controlled by the setting of the delay between the pulses. In our experiments, amorphous carbon films have been deposited in vacuum onto Si substrates by double pulses from a Ti:sapphire laser (180 fs, λ = 800 nm, at 1 kHz) and a KrF laser system (500 fs, λ = 248 nm, at 5 Hz). The intensities have been varied in the range of 3.4 × 10¹² to 2 × 10¹³ W/cm². The morphology and the main properties of the thin layers were investigated as a function of the time delay between the two ablating pulses (0-116.8 ps) and as a function of the irradiated area on the target surface. Atomic force microscopy, spectroscopic ellipsometry and Raman-spectroscopy were used to characterize the films. It was demonstrated that the change of the delay and the spot size results in the modification of the thickness distribution of the layers, and the carbon sp²/sp³ bonding ratio.     

Nuclear fusion from Coulomb explosions of deuterated methane clusters subjected to ultraintense femtosecond laser pulses

This paper reports that Coulomb explosions taken place in the experiment of heteronuclear deuterated methane clusters ((CD₄)₂) in a gas jet subjected to intense femtosecond laser pulses (170mJ, 70fs) have led to table-top laser driven DD nuclear fusion. The clusters produced in supersonic expansion had an average size of about 5nm in radius and the laser intensity used was 3×10¹⁷W/cm².The measured maximum and average energies of deuterons produced in the laser--cluster interaction were 60 and 13.5keV, respectively. From DD collisions of energetic deuterons, a yield of 2.5(±0.4)×10⁴ fusion neutrons of 2.45MeV per shot was realized, giving rise to a neutron production efficiency of about 1.5×10⁵ per joule of incident laser pulse energy. Theoretical calculations were performed and a fairly good agreement of the calculated neutron yield with that obtained from the present experiment was found.     

The dissociative recombination of HeNe+ ions with electrons: The partial rate constants for the formation of atoms in the 2p 53p configuration

A simple experiment transparent for interpretation is presented in which afterglow of a discharge in helium with a small admixture of neon was studied. The intensities of the spectral lines of the Ne* atom at the stage of plasma decay were analyzed to find the conditions under which the dissociative recombination of heteronuclear ions HeNe⁺ + e ?? He + Ne* played a predominant role in the formation of part of the after-glow spectrum. The absolute values of partial coefficients responsible for the formation of excited neon atoms in the 2p ⁵3p configuration were determined.     

Atom-dimer and dimer-dimer scattering in fermionic mixtures near a narrow Feshbach resonance

We develop a diagrammatic approach for solving few-body problems in heteronuclear fermionic mixtures near a narrow interspecies Feshbach resonance. We calculate s-, p-, and d-wave phaseshifts for the scattering of an atom by a weakly-bound dimer. The fermionic statistics of atoms and the composite nature of the dimer lead to a strong angular momentum dependence of the atom-dimer interaction, which manifests itself in a peculiar interference of the scattered s- and p-waves. This effect strengthens with the mass ratio and is remarkably pronounced in ⁴⁰K-(⁴⁰K-⁶Li) atom-dimer collisions. We calculate the scattering length for two dimers formed near a narrow interspecies resonance. Finally, we discuss the collisional relaxation of the dimers to deeply bound states and evaluate the corresponding rate constant as a function of the detuning and collision energy.     

Photon echo generated at the transition 0–1 in ytterbium vapor

Photon echo generated at the inter-combination transition (6s ²) ¹ S ₀ ? (6s6p) ³ P ₁ of ¹⁷⁴Yb was investigated for pure ytterbium vapor and for its mixtures with atomic buffers. In pure ytterbium vapor, the polarization of photon echoes at this 0?C1 transition coincides with the polarization of the second exciting pulse for all combinations of linear and circular polarizations of exciting radiation pulses. Photon echo does not appear either for linear orthogonal or for opposite circular polarizations of exciting pulses in pure ytterbium. In mixtures of ytterbium with atomic buffers (Kr, Xe), collision induced photon echo arises only for exciting pulses of linear orthogonal polarizations, its power is essentially less than that of the ordinary echo generated by pulses with parallel polarizations in the same mixture. Polarization of collision induced echo is linear, and it coincides with polarization of the first exciting pulse. Experimental results agree with calculations, and they confirm that the collision induced photon echo at this transition arises exclusively due to anisotropy of depolarizing collisions.     

Slice selection in solids by localized double-quantum coherence transfer

Double-quantum heteronuclear coherence transfer in solids shows a strong spatial dependence when performed in the presence of a magnetic field gradient. This is a direct consequence of the off-resonance sensitivity of the coherence transfer process and represents a new principle for localized NMR spectroscopy of quadrupole nuclei in solids. Since the slice-selective excitation is achieved simultaneously to the cross-polarization, the suggested pulse sequences avoid the use of shaped pulses, the application of which is problematic in solids. In the present work, the localization efficiency of this new slice-selection principle was analyzed in dependence on the experimental parameters for a spin system consisting of abundant spin-1/2 and rare spin-1 nuclei. The resulting slice profiles and the calculated dependences of the slice thickness for the basic coherence transfer procedures are discussed on the example of¹H?²H in monodeuterated benzene. The proposed method opens the possibility of volume-selective investigations of the structure and dynamics of materials using the well-established methodology of deuteron-NMR spectroscopy.     

Effect of the pulse leading-edge time on the dielectric strength of a vacuum gap

Optimal regimes for electrode conditioning in a vacuum by applying voltage pulses with different waveforms are considered. For nanosecond pulses with a constant duration (t _p = const), the impulse dielectric strength for an oblique voltage wave is shown to be more than four times higher than for a rectangular pulse with an infinitely short leading-edge duration. The dependences of the dielectric strength on the conditioning pulse duration in the range 10^?10 < t _p < 10^?3 s for pulses with different rise rates are obtained. The dielectric strength increases from 2 × 10⁷ V/m for microsecond pulses to 10¹⁰ V/m for subnanosecond pulses.     

Quantitative two-dimensional HSQC experiment for high magnetic field NMR spectrometers

The finite RF power available on carbon channel in proton–carbon correlation experiments leads to non-uniform cross peak intensity response across carbon chemical shift range. Several classes of broadband pulses are available that alleviate this problem. Adiabatic pulses provide an excellent magnetization inversion over a large bandwidth, and very recently, novel phase-modulated pulses have been proposed that perform 90° and 180° magnetization rotations with good offset tolerance. Here, we present a study how these broadband pulses (adiabatic and phase-modulated) can improve quantitative application of the heteronuclear single quantum coherence (HSQC) experiment on high magnetic field strength NMR spectrometers. Theoretical and experimental examinations of the quantitative, offset-compensated, CPMG-adjusted HSQC (Q-OCCAHSQC) experiment are presented. The proposed experiment offers a formidable improvement to the offset performance; ¹³C offset-dependent standard deviation of the peak intensity was below 6% in range of ±20 kHz. This covers the carbon chemical shift range of 150 ppm, which contains the protonated carbons excluding the aldehydes, for 22.3 T NMR magnets. A demonstration of the quantitative analysis of a fasting blood plasma sample obtained from a healthy volunteer is given.     

Recoupled Polarization-Transfer Methods for Solid-State H–C Heteronuclear Correlation in the Limit of Fast MAS

An in-depth account of the effects of homonuclear couplings and multiple heteronuclear couplings is given for a recently published technique for ¹H–¹³C dipolar correlation in solids under very fast MAS, where the heteronuclear dipolar coupling is recoupled by means of REDOR π-pulse trains. The method bears similarities to well-known solution-state NMR techniques, which form the framework of a heteronuclear multiple-quantum experiment. The so-called recoupled polarization-transfer (REPT) technique is versatile in that rotor-synchronized ¹H–¹³C shift correlation spectra can be recorded. In addition, weak heteronuclear dipolar coupling constants can be extracted by means of spinning sideband analysis in the indirect dimension of the experiment. These sidebands are generated by rotor encoding of the reconversion Hamiltonian. We present generalized variants of the initially described heteronuclear multiple-quantum correlation (HMQC) experiment, which are better suited for certain applications. Using these techniques, measurements on model compounds with ¹³C in natural abundance, as well as simulations, confirm the very weak effect of ¹H–¹H homonuclear couplings on the spectra recorded with spinning frequencies of 25–30 kHz. The effect of remote heteronuclear couplings on the spinning-sideband patterns of CH_n groups is discussed, and ¹³C spectral editing of rigid organic solids is shown to be practicable with these techniques.     

Electron-positron pair creation by powerful laser-ion interaction

Presently available high-power laser pulses of ponderomotive energy U _p ? 2mc ² should permit the fundamental processes of quantum electrodynamics in such fields, in particular, the formation of electron-positron pairs in impacts of laser pulses with highly charged ions, to be observed. We evaluate the highly nonlinear production rates of this process and investigate the most favorable conditions of pair production, in particular, either along the direction of linear polarization or in the propagation direction of the laser pulse. For femtosecond radiation pulses, it is possible to represent the laser beam by a monochromatic and linearly polarized electromagnetic plane wave. This approximation considerably simplifies the calculations required.     

Localized cross-polarization in solids

Single quantum heteronuclear cross-polarization in solids is strongly sensitive to resonance offsets. In the presence of main field- or radio-frequency field gradients, the cross-polarization efficiency, therefore, shows a strong spatial dependence, which represents a new principle for localized NMR in solids. Since slices-selective excitation is achieved simultaneously to cross-polarization, the suggested pulse sequences avoid the use of shaped pulses, the application of which is problematic with solid. The dependence of the localization efficiency on experimental and sample parameters is analyzed theoretically for a spin-1/2 system in the presence of a static or a radio-frequency magnetic field gradient. The resulting slice profiles and the calculated dependence of the slice thickness on the parameters of the basic cross-polarization procedures are discussed and confirmed experimentally on the example of¹H-³C spin systems.     

Deviations from Ohm's law for a metal at high current densities

High current pulses were generated in thin copper wires and the specific resistance for different current densities as the same temperature was determined. The measured values show an increase of resistance with current density reaching nearly a factor 3 at 1.6 × 10⁸A/cm²