Relaxation effects in two-dimensional zero-field nutation NQR spectroscopy

The relaxation and off-resonance effects on the NQR (nuclear quadrupole resonance) nutation frequency and on the damping constant of the nutation spectrum for spinsI = 3/2 are considered. Using the solution of dynamic equations for nuclear magnetisation in the rotating frame, we obtained a general expression for determination of the asymmetry parameter η, which includes the relaxation time and frequency offset. Specific requirements for the RF (radio frequency) field allowing the presence of nutation and the sufficient resolution of nutation spectra are determined. It is shown that at low RF field it is necessary to take into account theT ₂ relaxation effect on the location of frequency singularities in the nutation spectrum. The values ofH ₁ andT ₂ must be exactly known in nutation NQR spectroscopy. The 2D NQR spin-echo separation technique was used for determination of transverse relaxation of individual spin packets in case of inhomogeneously broadened NQR lines, so that the asymmetry parameter could then be determined by the nutation experiment with consideration of relaxation effects and frequency offset. The theoretical results are confirmed experimentally for the narrow and inhomogeneously broadened 2D-nutation NQR spectra in several molecular compounds containing the³⁵Cl and⁷⁵As nuclei.     

Sensitivity of two-dimensional NMR experiments for studying chemical exchange

The conditions required to optimize the sensitivity of two-dimensional experiments for the study of chemical exchange are discussed in detail and compared with results for selective saturation transfer experiments. Details of phase-cycling procedures are also given and a new method of data handling to produce pure absorption lineshapes is presented. The inherent sensitivity of two-dimensional spectra is compared with ordinary NMR spectra with particular regard to the significance of using discrete Fourier transforms. In conclusion, the superior sensitivity of two-dimensional methods over that of conventional techniques is demonstrated for the study of exchange processes in complex molecules.     

Multi-quantum echoes in GdAl2 zero-field high-resolution NMR

In this paper we present a series of high-resolution zero-field NMR spectra of the polycrystalline intermetallic compound GdAl₂. The spectra were obtained with the sample at 4.2 K in the ordered magnetic state and in the absence of an external static magnetic field. Using a sequence composed of two RF pulses, we obtained up to five multi-quantum echoes for the ²⁷Al nuclei, which were used to construct the zero-field NMR spectra. The spectra obtained from the FID observed after the second pulse and the even echoes exhibited higher resolution than the odd ones. In order to explain such behavior, we propose a model in which there are two regions inside the sample with different inhomogeneous spectral-line broadenings. Moreover, with the enhanced resolution from the FID signal, we were able to determine quadrupolar couplings with great precision directly from the respective spectra. These results were compared with those obtained from the quadrupolar oscillations of the echo signals, and showed good agreement. Similar data were also obtained from ¹⁵⁵Gd and ¹⁵⁷Gd nuclei.     

Dynamical exchange effects in a two-dimensional many-polaron gas

We calculate the influence of dynamical exchange effects on the response properties and the static properties of a two-dimensional many-polaron gas. These effects are not manifested in the random-phase approximation which is widely used in the analysis of the many-polaron system. Here they are taken into account by using a dielectric function derived in the time-dependent Hartree-Fock formalism. At weak electron-phonon coupling, we find that dynamical exchange effects lead to substantial corrections to the random-phase approximation results for the ground state energy, the effective mass, and the optical conductivity of the polaron system. Furthermore, we show that the reduction of the spectral weight of the optical absorption spectrum at frequencies above the longitudinal optical phonon frequency, due to many-body effects, is overestimated by the random-phase approximation.Received: 24 December 2003, Published online: 9 April 2004PACS: 71.45.Gm Exchange, correlation, dielectric and magnetic response functions, plasmons - 71.10.Pm Fermions in reduced dimensions (anyons, composite fermions, Luttinger liquid, etc.) - 71.38.Fp Large or Fröhlich polarons     

Theory of zero-field NMR spectra. Effects of motion

Zero-field NMR spectra of tunnelling methyl group, classically reorienting methyl group and of a pair of spins 1/2 jumping between two perpendicular orientations are calculated. A formula for the second moment of a rigid lattice is derived from a formal analogy between zero-field and high-field spectra. Fast reorientation about a perpendicular axis reduces the intramolecular second moment to 1/4 of its rigid value. The zerofield method seems to be a promising tool for the determination of tunnelling splitting or of jumping rates.     

Dual processing of two-dimensional exchange data in magic angle spinning NMR of solids.

We discuss procedures for processing data in rotor-synchronized two-dimensional magic angle spinning (2D MAS) NMR exchange measurements for both structural and dynamical studies. We show, both mathematically and experimentally, that there are two distinct data processing procedures that lead to 2D MAS exchange spectra with purely absorptive crosspeaks. One procedure is that described previously by Hagemeyer, Schmidt-Rohr, and Spiess (HSS). The other procedure is related, but different, and leads to crosspeak intensities given by the formulae of Herzfeld, Roberts, and Griffin (HRG). In 2D MAS exchange experiments on doubly (13)C-labeled l-alanylglycylglycine, we demonstrate that the HSS and HRG crosspeak intensities can be extracted separately from the same data set and contain independent information. Processing and analysis of 2D MAS exchange data with both the HSS and the HRG procedures may enhance utilization of the information content of 2D MAS exchange measurements.     

Chemical exchange in KHSeO4 and NH4HSeO4 studied by two-dimensional NMR

The microscopic mechanism of proton transport in partially deuterated potassium hydrogen selenate (KHSe) and in partially deuterated ammonium hydrogen selenate (AHSe) were studied by means of one-dimensional Fourier transform²H nuclear magnetic resonance (NMR), two-dimensional²H NMR and dielectric measurements over a wide temperature range. In both systems, KHSe and AHSe, the slow chemical exchange processes of deuterons between different hydrogen bridges occur. It was established that the rates of exchange between deuteron sites, which are involved in infinite chains of hydrogen bonds, are approximately the same for both crystals. The rates of exchange between these positions and the deuterons in the dimer groups of KHSe are approximately hundred times more slowly. On the basis of our findings, we discuss the models of the microscopic mechanism of hydrogen transport for both substances.     

Large exchange bias after zero-field cooling from an unmagnetized state

Exchange bias (EB) is usually observed in systems with an interface between different magnetic phases after field cooling. Here we report an unusual phenomenon in which a large EB can be observed in Ni-Mn-In bulk alloys after zero-field cooling from an unmagnetized state. We propose that this is related to the newly formed interface between different magnetic phases during the initial magnetization process. The magnetic unidirectional anisotropy, which is the origin of the EB effect, can be created isothermally below the blocking temperature.     

Derivation and evaluation of the fourth moment of NMR lineshape in zero-field

An expression for the fourth moment in zero-field NMR has been analytically derived and numerically evaluated for a rigid cubic lattice. Model simulations have been performed to calculate the second moment, the fourth moment, the ratio of the fourth moment to the square of the second moment, and the width of the resonance line for a crystal and a polycrystalline material in high-field as well as in zero-field NMR. The simulation results allow us to draw two conclusions: (1) zero-field NMR gives sharper and better defined spectra than the high-field NMR and (2) the ratio of the high- to zero-field resonance line-widths is 4 for a crystal, whereas it is 11 for a polycrystalline material.     

Dynamical exchange effects in the dielectric function of the two-dimensional electron gas

Dynamical exchange interactions can be introduced in the dielectric function via a dynamic local field factor. We study the effects of this inclusion on both the static and the frequency dependent dielectric function of a two-dimensional electron gas, using the dynamic local field factor that we derived recently via the dynamical exchange decoupling method. The results are compared with the dielectric function in the Random Phase Approximation and with different dynamic and static approximations of the local field factor.Received: 7 May 2003, Published online: 22 September 2003PACS: 71.45.Gm Exchange, correlation, dielectric and magnetic response functions, plasmons - 77.22.Ch Permittivity (dielectric function) - 77.55.+f Dielectric thin filmsJ.T. Devreese: , jtd@uia.ua.ac.be     

Rate constants for chemical exchange between water and hydroxyl protons in natural compounds evaluated with NMR two-dimensional exchange spectroscopy and geometric average method

Nuclear magnetic resonance two-dimensional exchange spectroscopy has been applied to measure the chemical exchange rate constants between water and hydroxyl protons in three natural organic compounds which contain four to eight hydroxyl groups. In data treatment, the simple geometric average method has been used. Application of the geometric average method to assumed exchange systems has indicated that the method is reliable.     

Separation and suppression of coherent transfer effects in two-dimensional NOE and chemical exchange spectroscopy

A new method for the separation of coherent and incoherent magnetization transfer in two-dimensional (2D) NOE and chemical exchange spectroscopy is described. The new experiment differs from previous 2D exchange experiments, in that the mixing time τ_m is incremented systematically together with the evolution time t₁. This permits the distinction of the different orders of multiple-quantum coherence during the mixing time and allows the separation of coherent and incoherent transfer processes. The resulting clarification of chemical exchange and 2D NOE spectra is illustrated with experiments on small molecules and on a globular protein, the basic pancreatic trypsin inhibitor.     

Inverse methods in two-dimensional NMR spectral analysis

Solid-state NMR is a valuable technique for the study of disordered materials. Analysis of such spectra usually involves solution of so-called ill-posed inverse problems. Here we present a strategy for the analysis of two-parameter two-dimensional NMR problems and test it on 2D DECODER and DOQSY experiments. Using Monte Carlo tests, constraints are determined for the resolution and accuracy of the analysis for both experiments. The methods are finally applied to spectra of spider dragline silk, a heterogeneous solid fibrous protein.     

Time-domain calculation of chemical exchange effects in the NMR spectra of rotating solids.

A simple method is described for the calculation of magic-angle-spinning (MAS) spectra of solids in the presence of chemical exchange. The method converges quickly, allowing rapid calculation of the spectra. Calculated spectra are given for molecular motion involving 2 and 6 sites.     

Off-resonance effects of the radiofrequency pulses used in spectral editing with double-quantum coherence transfer

Spectral editing using gradient selected double-quantum (DQ) coherence transfer is often used for the selective observation of metabolites in vivo. In attempting to optimize the detection sensitivity of a conventional DQ spectral editing sequence, the effects of using radiofrequency (RF) pulses that are not at the resonance frequency of the observed peaks were investigated both theoretically and experimentally. The results show that spectral editing using pulses at the frequency of the observed resonance does not necessarily give the optimal detection sensitivity. At 7 T, the detection sensitivity of lactate observed using a DQ editing method can be increased by up to 30% by setting the RF pulses off resonance at the proper frequency. The results also suggest that slice selective RF pulses used in DQ spectral editing combined with PRESS localization may have slice profiles different from those when the same pulses are used for standard PRESS spatial localization.