Localized double-spin-echo proton spectroscopy of weakly coupled homonuclear spin systems

The effect of localized double-spin-echo spectroscopy (PRESS) on a homonuclear weakly coupled AX spin system was calculated by the use of the product-operator formalism. Due to flip-angle distributions within the excited slices, different unwanted coherences are created which give rise to signal losses after the second and third RF pulse. The amount of signal loss is dependent on the timing of the sequence; i.e., only a proper choice of the time intervals between the pulses results in a high signal strength for coupled spins. Experiments were carried out on a Siemens Magnetom 1.5 T whole-body imager to verify the theory. Signal gains of far more than 100% were obtained for the coupled spins of lactate.     

Kinetics of the polarization transfer in spatially disordered spin systems: Depolarization of impurity beta-active nuclei

We performed theoretical and experimental studies of the delocalization of the nuclear polarization of impurity beta-active nuclei ⁸Li in the spatially disordered system of ⁶Li nuclei in LiF single crystals. The process is controlled by the dipole-dipole interaction of nuclear magnetic moments with other nuclei (⁷Li, ¹⁹F) in the crystal. It is effective in a wide range of magnetic fields H ₀ = 150–3000 G as a result of a unique proximity of the g-factors of ⁸Li and ⁶Li nuclei: (g(⁸Li) − g(⁶Li))/g(⁶Li) = 0.0057. The kinetics of the ⁸Li depolarization is measured for an ⁶Li concentration of 0.15%–10.06% and in the field H ₀ of 200, 692 and 1210 G. A satisfactory explanation of the results is obtained on the basis of a numerical-analytical simulation of the process.     

A pulse sequence for averaging the strong homonuclear scalar coupling in AB spin systems

A pulse sequence is proposed for the suppression of the strong homonuclear scalar coupling in the case of AB spin systems. The theoretical treatment is presented in terms of the average Hamiltonian theory in the case of aperiodic perturbations. The zero-order and the first-order correction terms in the full average Hamiltonian are calculated. It is shown that the chemical shift interaction for one of the spins is completely refocused and the conditions in which the interactions bilinear in spin operators are efficiently suppressed are analyzed.     

One-dimensional homonuclear polarization transfer. Studies of parameters which affect intensities in the SPI NMR technique

A study is presented of the effects of strong scalar coupling and of the angle of the nonselective observing pulse, as well as of the effects of selective pulses, in one-dimensional selective population inversion (SPI) experiments of homonuclear spin systems. Density matrix computer simulations, which also take into account relaxation effects, of {A}-B SPI experiments, and for comparison also of {A}-X, reproduce different aspects of the experimental spectra. An insight is therefore offered into the parameters which affect intensities in the SPI one-dimensional NMR technique for homonuclear polarization transfer.     

Thermoelectric response of spin polarization in Rashba spintronic systems

Motivated by the recent discovery of a strongly spin–orbit-coupled two-dimensional (2D) electron gas near the surface of Rashba semiconductors BiTeX (X= Cl, Br, I), we calculate the thermoelectric responses of spin polarization in a 2D Rashba model. By self-consistently determining the energyand band-dependent transport time, we present an exact solution of the linearized Boltzmann equation for elastic scattering. Using this solution, we find a non-Edelstein electric-field-induced spin polarization that is linear in the Fermi energy E_F when E_F lies below the band crossing point. The spin polarization efficiency, which is the electric-field-induced spin polarization divided by the driven electric current, increases for smaller E_F .We show that, as a function of E_F, the temperaturegradient-induced spin polarization increases continuously to a saturation value when EF decreases below the band crossing point. As the temperature tends to zero, the temperature-gradient-induced spin polarization vanishes.     

Spin dynamics of polarization inversion spin exchange at the magic angle in multiple spin systems

Polarization inversion spin exchange at the magic angle (PISEMA) [J. Magn. Reson. A 109, 270 (1994)] is an important experiment in NMR structural characterization of membrane proteins in oriented lipid bilayers. This paper presents a theoretical and experimental study of the spin dynamics in PISEMA to investigate the line-narrowing mechanism. The study focuses on the effect of neighboring protons on the spin exchange of a strongly coupled spin pair. The spin exchange is solved analytically for simple spin systems and is numerically simulated for many-spin systems. The results show that the dipolar couplings from the neighboring protons of a strongly coupled spin pair perturb the spin exchange only in the second order, therefore it has little contribution to the linewidth of PISEMA spectra in comparison to the separated-local-field spectra. The effects from proton resonance offset and the mismatch of the Hartmann-Hahn condition are also discussed along with experimental results using model single-crystal samples.     

Capacitance spectroscopy investigation of the spin polarization of two-dimensional electronic systems

It is shown that capacitance spectroscopy can be used to investigate the spin polarization of two-dimensional electronic systems (2DESs). We employed this method to investigate the spin polarization of 2DESs in a GaAs/AlGaAs heterojunction for filling factors of the magneticquantization levels 0.28<ν<0.9. It is proved that in the presence of states of the fractional quantum Hall effect with ν _f =1/3 and 2/3 the ground state of a 2DES with ν>2/3 is incompletely spin-polarized. Pis’ma Zh. éksp. Teor. Fiz. 65, No. 1, 102–107 (10 January 1997)     

Multiple-quantum cross polarization in quadrupolar spin systems during magic-angle spinning

We describe the concept of multiple-quantum cross polarization (CP) between an I = 32 and an I = 12 spin during magic-angle spinning. Experimental and theoretical results for (23)Na-(1)H pairs are presented that elucidate the transfer mechanism and the beneficial effect of adiabatic amplitude modulations of the CP field. The multiple-quantum CP approach is shown to be beneficial for improving the sensitivity of CP-MQMAS experiments and for detecting dipolar correlations.     

Classical and thermodynamic limits for generalised quantum spin systems

We prove that the rescaled upper and lower symbols for arbitrary generalised quantum spin systems converge in the classical limit. For a large class of models this enables us to derive the asyptotics of quantum free energies in the classical and in the thermodynamic limit.Research supported by a European Science Exchange Fellowship of the Royal Society, London     

Optimization of INEPT and DEPT experiments for spin systems with hetero- and homonuclear couplings

The application of INEPT and DEPT pulse sequences to weakly coupled spin-$\text{1}\text{2}$ systems with different hetero- and homonuclear coupling constants has been investigated. For the simulation of the spectra arising from these multiple-pulse experiments, general computer programs have been written based on the density matrix approach. Numerical results calculated in this way allow the investigation of the polarization transfer in detail. Analytical expressions which describe the attainable sensitivity enhancement are presented. Their use in the experimental optimization of these pulse sequences is demonstrated for ¹³C and ¹⁵N NMR spectra.     

Efficient spin-spin scalar coupling mediated C-13 homonuclear polarization transfer in biological solids without proton decoupling

We demonstrate that an efficient C′↔C polarization transfer based on J-coupling can be realized under fast magic-angle spinning (MAS) condition without ¹H decoupling. Experimental results are presented for model crystalline compounds as well as a non-crystalline 17-residue polypeptide MB(i+4)EK. Measurements on MB(i+4)EK demonstrate that 53% of the initial C′ polarization was transferred to the cross peaks at 7.05 T under 25 kHz MAS spinning.     

Effect of spin relaxation on the polarization of excitonic luminescence in disordered systems

The kinetics of localized excitons in systems with disorder is studied with allowance for the fine structure of the excitonic state and for spin relaxation processes. The exciton distribution function, formed as a result of the competition between radiative and nonradiative recombination, spin relaxation, and intercenter transitions with an exponentially wide scatter in transition times, is calculated. Pis’ma Zh. éksp. Teor. Fiz. 65, No. 8, 612–617 (25 April 1997)     

Solid-state NMR spectroscopy using the lost I spin magnetization in polarization transfer experiments

A variation of the cross polarization (CP) experiment is discussed. The method requires two scans where the difference signal is equivalent to the I spin magnetization that is transferred to the S spins. The acquired signal is equivalent to F1 sum projection of a two-dimensional (2D) heteronuclear correlation experiment and is obtained by just two scans without the need to increment the indirect time domain t(1). Any polarization transfer method and any kind of spin manipulations during the t(1) incrementation period of a 2D NMR experiment can be applied. The method allows fast measurements of the CP transfer, particularly if various S spins signal overlap and is good for spectral editing of I spin signals with contact to S spins. Various examples for biomaterials are presented. Most importantly, this novel approach is ideal for detailed investigations of organic-mineral interfaces in bone, here demonstrated for O-phospho-l-serine as simple model compound.     

Intersubband magnetoplasmon as a detector of the spin polarization in two-dimensional electron systems

The magnetic field dynamics of intersubband collective excitations in two-dimensional electron systems based on Mg _x Zn_1-x O/ZnO heterostructures is studied by the Raman scattering method. It is found that, upon the change in the spin polarization under conditions of the transition from the filling factor ν = 2 to ν = 1, the energy of the intersubband magnetoplasmon changes considerably. The performed theoretical analysis shows that this effect is attributed to the concomitant change in the exchange interaction in the excitation energy.     

Incorporating homonuclear polarization transfer into PRESS for proton spectral editing: illustration with lactate and glutathione

A proton spectral editing pulse sequence for the detection of metabolites with spin systems that involve weak coupling is presented. The sequence is based on homonuclear polarization transfer incorporated into the standard PRESS (Point RESolved Spectroscopy) sequence, which is a volume-selective double spin echo method, to enable spatial localization. All peaks in the region of interest are initially suppressed whether they are peaks from the target metabolite or from contaminating background. The target signal is then restored by polarization transfer from a proton that has a resonance outside the suppressed region and to which the target spins are weakly coupled. This is achieved by the application of a 90 degrees hard pulse with phase orthogonal to that of the PRESS excitation pulse at the location of the first echo in PRESS and by optimizing the two PRESS timings, TE(1) and TE(2), for most efficient yield. Background signal not coupled to any protons outside the initially saturated region remains suppressed. The advantage of this sequence compared to multiple quantum filters is that signal from singlet peaks outside the suppressed area are preserved and can thus be used as a reference. The efficacy of the sequence was verified experimentally on phantom solutions of lactate and glutathione at 3.0 T. For the AX(3) spin system of lactate, the sequence timings were optimized by product operator calculations whereas for the ABX spin system of the cysteinyl group of glutathione numerical calculations were performed for sequence timing optimization.     

Possible evidence of a spontaneous spin polarization in mesoscopic two-dimensional electron systems

We have experimentally studied the nonequilibrium transport in low-density clean two-dimensional (2D) electron systems at mesoscopic length scales. At zero magnetic field (B), a double-peak structure in the nonlinear conductance was observed close to the Fermi energy in the localized regime. From the behavior of these peaks at nonzero B, we could associate them with the opposite spin states of the system, indicating a spontaneous spin polarization at B=0. Detailed temperature and disorder dependence of the structure shows that such a splitting is a ground-state property of low-density 2D systems.     

Transverse magnetization transfer under planar mixing conditions in spin systems consisting of three coupled spins 1/2

Polarization transfer under planar mixing conditions is a widely used tool in modern NMR-experiments. In the case of two coupled spins 1/2 or a chain of three or more spins 1/2 with only nearest neighbor couplings, it is only possible to transfer a single magnetization component (longitudinal magnetization in the principle axis system of the planar coupling tensors). However, if all couplings in a three-spin system are non-zero, it turns out that all magnetization components can be efficiently transferred even under strictly planar mixing conditions. In this article a detailed theoretical analysis is presented based on analytical transverse coherence transfer functions and on the underlying commutator algebra. In addition, transverse magnetization transfer is demonstrated experimentally. The results show that in highly coupled spin systems, as for example in the case of partially aligned samples with many residual dipolar couplings, special care has to be taken to avoid phase distortions if planar mixing steps are used.