Separation of quadrupolar and magnetic contributions to spin-lattice relaxation in the case of a single isotope

We present a NMR pulse double-irradiation method which allows one to separate magnetic from quadrupolar contributions in the spin–lattice relaxation. The pulse sequence fully saturates one transition while another is observed. In the presence of a Δm = 2 quadrupolar contribution, the intensity of the observed line is altered compared to a standard spin-echo experiment. We calculated analytically this intensity change for spins I = 1, , , thus providing a quantitative analysis of the experimental results. Since the pulse sequence we used takes care of the absorbed radiofrequency power, no problems due to heating arise. The method is especially suited when only one NMR sensitive isotope is available. Different cross-checks were performed to prove the reliability of the results obtained. The applicability of this method is demonstrated by a study of the plane oxygen ¹⁷O (I = ) in the high-temperature superconductor YBa₂Cu₄O₈: the ¹⁷O spin–lattice relaxation rate consists of magnetic as well as quadrupolar contributions.     

Spin-lattice relaxation enhancement in liquid gallium confined within nanoporous matrices

Nuclear spin relaxation for liquid gallium embedded into nanoporous matrices was found to accelerate remarkably compared to the bulk melt. NMR measurements on two gallium isotopes showed that the dominant mechanism of relaxation was changed from magnetic to quadrupolar and the relation rate depended on the Larmor frequency. The correlation time of electric field gradient fluctuations was estimated using data for quadrupolar relaxation contribution and was found to increase drastically compared to bulk, which corresponded to slowing down mobility in confined liquid gallium.     

Electric quadrupolar contribution to the nuclear spin-lattice relaxation of Ir in Fe

We report on the first quantitative determination of the electric quadrupolar contribution to the nuclear spin-lattice relaxation in a transition metal. For 186Ir and 189Ir in Fe we have determined the magnetic and the electric quadrupolar part of the relaxation for magnetic fields between 0.01 and 2 T. The quadrupolar part gives information on the role of the orbital motion of the electrons for the relaxation process. Our results prove that the unexpected high relaxation rates in Fe and their magnetic field dependence are due to a nonorbital relaxation mechanism.     

High-field QCPMG NMR of large quadrupolar patterns using resistive magnets

Spectroscopy in a high magnetic field reduces second-order quadrupolar shift while increasing chemical shift. It changes the scale between quadrupolar and chemical shift of half-integer quadrupolar spins. The application of QCPMG multiple echo for acquiring large quadrupolar pattern under the high magnetic field of a 25 T resistive magnet is presented for acquiring large quadrupolar patterns. It shows that temporal field fluctuations and spatial homogeneity of the Keck magnet at the NHMFL contribute about ±20 ppm in line broadening. NMR patterns which have breadths of hundreds to thousands of kilohertz can be efficiently recorded using a combination of QCPMG and magnetic field stepping with negligible hindrance from the inhomogeneity and field fluctuations of powered magnets.     

Quadrupole relaxation enhancement--application to molecular crystals

A general theory of field dependent spin-lattice relaxation for nuclei of the spin quantum number 1/2 (1H, 19F, 13C) caused by dipole-dipole interactions with neighboring quadrupolar nuclei (nuclei possessing a quadrupolar moment) is presented. The theory is valid for arbitrary motional conditions and should be treated as a quadrupolar counterpart of the paramagnetic relaxation enhancement theory. When the energy level splitting of the dipolar spin (I=1/2) matches one of the transition frequencies of the quadrupolar nuclei one can observe a local enhancement of the dipolar spin relaxation (referred to as "quadrupolar peaks"). To see such effects the dynamics modulating the spin interactions has to be relatively slow. This brings the system beyond the validity range of perturbation approaches and requires the stochastic Liouville equation to be applied. The presented theory describes the quadrupolar relaxation enhancement (QRE) for an arbitrary spin quantum number of the quadrupolar nuclei and includes the asymmetry of the quadrupolar coupling. It has been applied to interpret the shape of magnetization curves (amplitude of 1H magnetization versus magnetic field) for the molecular crystal [C3N2H5]6[Bi4Br18] ([C3N2H5]-imidazolium). The magnetization curves show several dips (local minima) attributed to 1H-14N quadrupolar relaxation enhancement effects. In addition, as a limiting case a perturbation approach to QRE has been presented and its validity conditions have been discussed.     

Nuclear quadrupolar relaxation in ionic crystals

The nuclear quadrupolar relaxation time of alkali halide crystals is investigated by the Heitler-London approximation. We use the Slater determinant which is constructed by the Hartree-Fock wave functions of the free ions. The charge distribution around an ion is not spherically symmetrical because of mutual overlap of the atomic wave functions of nearest-neighbor ions. Moreover, the charge distribution around an ion changes its shape during thermal vibrations of the ions, because the degree of the overlap depends upon the distance apart of the ions. Therefore, the quadrupolar interaction in alkali halide lattices is the resultant of a combination of the thermal vibration with the charge overlap. As illustrations of the theory, we have computed the quadrupolar relaxation time of the ³⁹K and the ³⁵Cl nuclei in the KCl crystal, and the ²³Na nucleus in the NaCl crystal. The theoretical results are in good agreement with those of experiments. We have also computed the ratio of the quadrupolar relaxation time of the metal nucleus to that of the halogen nucleus for some alkali halide crystals. After computing the same ratio by the covalent model and the deformation model, we have compared these results with the available experimental data. Finally, by using the same overlap model as that mentioned previously, we have developed a formula which gives the chemical shift of ionic crystals.     

Quantitative analysis of 17O exchange and T1 relaxation data: application to zirconium tungstate

The theoretical basis behind a recent quantitative analysis of 17O exchange in ZrW2O8 [M.R. Hampson, J.S.O. Evans, P. Hodgkinson, J. Am. Chem. Soc. 127 (2005) 15175-15181] is set out. Despite the complexities of combining the multi-exponential relaxation of half-integer quadrupolar nuclei with chemical exchange, it is shown how magnetisation transfer experiments can be analysed to obtain estimates of absolute exchange rates. The multi-exponential relaxation is best modelled using a magnetic mechanism, i.e. the rapid T1 relaxation observed, particularly at high temperatures, can be directly related to the relatively high degree of 17O labelling employed. The combination of the 1D EXSY results with T1 values as a function of temperature provides exchange rates and activation barriers over a wide temperature range (40-226 degrees C).     

Electric quadrupole interactions and the γ–α phase transition in Ce: the role of conduction electrons

We present a theoretical model of the “isostructural" - phase transition in Ce which is based on quadrupolar interactions due to coupled charge density fluctuations of 4f electrons and of conduction electrons. The latter are treated in tight-binding approximation. The - transition is described as an orientational ordering of quadrupolar electronic densities in a structure. The quadrupolar order of the conduction electron densities is complementary to the quadrupolar order of 4f electron densities. The inclusion of conduction electrons leads to an increase of the lattice contraction at the - transition in comparison to the sole effect of 4f electrons. We calculate the Bragg scattering law and suggest synchrotron radiation experiments in order to check the structure. Received 21 September 1999 and Received in final form 2 May 2000     

NMR study of the magnetic properties of the polymerized phase of Cs1C60

\chem{Cs_{1}C_{60}} . The NMR spectrum allows, when the Magic Angle Spinning (MAS) technique is used, to get information about the electronic structure of this phase, which points out that the spin density is not uniformly distributed on the ball. An estimation of the strength of the quadrupolar effects on is then given, which shows that it is possible to analyse the spin-lattice relaxation time in terms of magnetic effects. A comparison with the of is then justified and allows us to point out the importance of low dimensional antiferromagnetic fluctuations in this compound. We also investigate the nature of the magnetic ground state in : the broadening of the spectra states unambiguously its magnetic nature and a detailed analysis of their shape gives further indications on the antiferromagnetic nature of the magnetic order, which seems characterized by a large amount of disorder. Received: 19 November 1996/Accepted: 19 December 1996     

Dynamics of the local moment induced by nonmagnetic defects in cuprates

We present a study of the spin dynamics of magnetic defects induced by Li substitution of the plane Cu in the normal state of YBa2Cu3O6+x. The fluctuations of the coupled Cu magnetic moments in the vicinity of Li are probed by near-neighbor 89Y and 7Li NMR spin lattice relaxation. The data indicate that the magnetic perturbation fluctuates as a single entity with a correlation time tau which scales with the local static susceptibility. This behavior is reminiscent of the low T Kondo state of magnetic impurities in conventional metals. Surprisingly it extends well above the "Kondo" temperature for the underdoped pseudogapped case.     

93Nb and 17O NMR chemical shifts of niobiophosphate compounds

Niobiophosphate compounds with a large range of niobium and oxygen environments were studied with (93)Nb and (17)O solid-state NMR. (93)Nb isotropic chemical shift of pure niobate Nb(ONb)(6), pure phosphate Nb(OP)(6) and mixed phosphate-niobate Nb(OP)(x)(ONb)((6-x)) (1相似文献   

Non-linear spin fluctuations and phase transitions in itinerant electron magnets: CMR manganites

We present a review analyzing the effects of coupling of transverse magnons with longitudinal spin fluctuations in isotropic itinerant ferro- and antiferromagnets. It is shown that this coupling essentially changes the spectrum of longitudinal fluctuations. At low-temperatures their spectrum is dominated by the linear Landau relaxation, is purely quasielastic and described by a broad central peak of a paramagnon type. On approaching the critical temperature non-linear magnetic relaxation due to mode–mode couplings can dominate and lead to a rapid increase of the central peak and to a new mechanism of magnetic phase transitions governed by non-linear spin fluctuations. The formalism is applied to the CMR manganites where the observed quasielastic fluctuations can be viewed as non-linear spin-lattice fluctuations strongly affected by magnons.     

Nuclear quadrupole resonance studies of transparent conducting oxides

We report ^63,65Cu spin–lattice relaxation rates measured by nuclear quadrupole resonance (NQR) in the delafossite compound CuYO₂ and CuYO₂:Ca over a temperature range from 200 to 450 K. CuYO₂:Ca is a prototype transparent oxide exhibiting p-type electrical conductivity. Relaxation rates in CuYO₂:Ca are enhanced by one to two orders of magnitude relative to undoped material, exhibit much stronger temperature dependence, and contain contributions from magnetic and quadrupolar relaxation mechanisms with roughly equal strengths. Relaxation in undoped CuYO₂ is of purely quadrupolar origin and is attributed to interactions with lattice phonons. The main focus of this paper is the magnetic contribution to the relaxation rate in CuYO₂:Ca which is attributed to the hyperfine fields of carriers. It is argued that the dynamics of the hyperfine field are dominated by the hopping rate for carrier transfers between neighboring atoms in the copper planes of the delafossite structure. Comparison of the magnetic relaxation rates with the DC conductivity permits an estimate of the carrier concentration and mobility.     

Dipole-quadrupole force ratios determine the ability of potential models to describe the phase diagram of water

We show that, in order to yield an acceptable phase diagram for water, the key ingredient is the relative strength of the dipolar and quadrupolar forces. We also demonstrate that for three-point-charge water models the relative strength of the dipolar to quadrupolar forces is determined by the position of the negative charge. This provides a theoretical background--supported by the experiment--to our knowledge of the water interactions which at present is essentially dominated by empirical models. In addition, it can be quite useful in the development of improved water models with a more physical basis.     

Magnetization-recovery experiments for static and MAS-NMR of I=3/2 nuclei

Multifrequency pulsed NMR experiments on quadrupole-perturbed I=3/2 spins in single crystals are shown to be useful for measuring spin-lattice relaxation parameters even for a mixture of quadrupolar plus magnetic relaxation mechanisms. Such measurements can then be related to other MAS-NMR experiments on powders. This strategy is demonstrated by studies of (71)Ga and (69)Ga (both I=3/2) spin-lattice relaxation behavior in a single-crystal (film) sample of gallium nitride, GaN, at various orientations of the axially symmetric nuclear quadrupole coupling tensor. Observation of apparent single-exponential relaxation behavior in I=3/2 saturation-recovery experiments can be misleading when individual contributing rate processes are neglected in the interpretation. The quadrupolar mechanism (dominant in this study) has both a single-quantum process (T(1Q1)) and a double-quantum process (T(1Q2)), whose time constants are not necessarily equal. Magnetic relaxation (in this study most likely arising from hyperfine couplings to unpaired delocalized electron spins in the conduction band) also contributes to a single-quantum process (T(1M)). A strategy of multifrequency irradiation with observation of satellite and/or central transitions, incorporating different initial conditions for the level populations, provides a means of obtaining these three relaxation time constants from single-crystal (71)Ga data alone. The (69)Ga results provide a further check of internal consistency, since magnetic and quadrupolar contributions to its relaxation scale in opposite directions compared to (71)Ga. For both perpendicular and parallel quadrupole coupling tensor symmetry axis orientations small but significant differences between T(1Q1) and T(1Q2) were measured, whereas for a tensor symmetry axis oriented at the magic-angle (54.74 degrees ) the values were essentially equal. Magic-angle spinning introduces a number of complications into the measurement and interpretation of the spin-lattice relaxation. Comparison of (71)Ga and (69)Ga MAS-NMR saturation-recovery curves with both central and satellite transitions completely saturated by a train of 90 degrees pulses incommensurate with the rotor period provides the simplest means of assessing the contribution from magnetic relaxation, and yields results for the quadrupolar mechanism contribution that are consistent with those obtained from the film sample.     

Linear chain antiferromagnetism in FeOHSO4

Magnetic susceptibility measurements on Fe OH SO₄ suggest linear chain antiferromagnetism up to at least 200°K with a transition to three dimensional antiferromagnetism at 56°K. Mössbauer spectra show magnetic hyperfine splitting up to ～ 90°K and this is interpreted in terms of intrachain spin correlation with relaxation effects caused by interchain spin relaxation. The 4·2°K spectrum is strongly asymmetric because of the admixture of nuclear eigenfunctions by non-parallel magnetic and quadrupolar principal axes systems. Using this the first complete derivation of a complete set of hyperfine interaction parameters from a Mössbauer spectrum is made and correlated with the crystallographic structure.     

Framework and extra-framework aluminium in wet ion exchanged Fe-ZSM5 and the effect of steam during the decomposition of N2O

The role of extra-framework and framework aluminium in wet-ion exchanged Fe-ZSM5 has been studied using ²⁹Si NMR and ²⁷Al triple quantum magic angle spinning (3QMAS) NMR. A series of samples were studied, the parent material, the wet ion exchanged Fe-ZSM5 and Fe-ZSM5 that has been used in the decomposition of N₂O with varying reaction conditions. Various framework and extra-framework aluminium species have been identified. It was found that cationic Fe species prefer to replace the Brønsted acid protons in their charge balancing role at those aluminium sites associated with the largest quadrupolar product. The framework aluminium atoms that pertain to the smaller quadrupolar product, which are either charge balanced by extra-framework aluminium or a proton, are much less prone to exchange. In the catalytic decomposition of N₂O it seemed that water present in small amounts enhances the catalytic activity. However, water also decreases the long term stability and performance by dealuminating the zeolite framework. With a high amount of water present, Fe-ZSM5 was destabilised and catalytically inferior.     

Magnetic and electronic properties of hexairon(III) nanocluster with cyclic structure: a Mössbauer study

A molecular cluster containing a coplanar ring of iron(III) ions with spin 5/2 was investigated by Mössbauer spectroscopy. The iron spins are antiferromagnetically coupled so that the ground state has total spin S=0. Spectra in the absence of an applied magnetic field consisted of a quadrupolar doublet, the linewidth of which monotonically increased with the temperature. A quadrupolar splitting of about 0.35 mm/s was found. Calculations of the ironorbital electronic populations were carried out and the quadrupolar splitting was estimated. Its value was in agreement with the experimental one. In addition, the trend of the linewidth was explained in terms of isotropic spin fluctuations. Spectra in the presence of a 4.5 T longitudinal magnetic field were also collected. The hyperfine field was obtained from their fitting. Differences with respect to the hyperfine field obtained from susceptibility data were also interpreted in terms of spin fluctuations.     

Pronounced in-plane anisotropy of phonon anomalies in YBa(2)Cu(3)O(6.6)

The dispersion of the Cu-O bond-stretching and bond-bending vibrations in YBa(2)Cu(3)O(6.6) has been studied by high resolution inelastic neutron scattering. While the behavior of the bond-bending vibrations can be well accounted for by a simple potential model, the bond-stretching vibrations show a highly anomalous behavior. The displacement pattern of the most anomalous phonons is in principle consistent with dynamic charge stripe formation. However, charge stripes would have to extend along the a axis and not the b axis as inferred from the magnetic fluctuations by Mook et al. [Nature (London) 404, 729 (2000)].