NMR of 27 Al in paramagnetic single-crystal DyAl2

NMR of ²⁷Al was observed in a spherical single crystal of DyAl₂ in the paramagnetic state. The well split quadrupole spectrum yielded a quadrupole frequency ν_Q = 561 kHz and hyperfine constant H_hf^p = -3.17 kOe/n_B. The anisotropy of the spectrum is well explained by the dipolar interaction.     

A Definitive Example of Aluminum-27 Chemical Shielding Anisotropy

Solid-state²⁷Al NMR spectra have been obtained for a crystalline 1:1 complex of AlCl₃and OPCl₃. Aluminum chloride phosphoryl chloride, AlCl₃· OPCl₃(1), is unusual in that the Al–O–P bond angle is close to 180°. From analysis of the²⁷Al MAS NMR spectra, it was determined that the²⁷Al nuclear quadrupole coupling constant is 6.0(1) MHz, the asymmetry in the electric field gradient (efg) tensor is 0.15(2), and the isotropic chemical shift, δ_iso(²⁷Al), is 88(1) ppm. Solid-state²⁷Al NMR of a stationary sample reveals a line shape affected by a combination of anisotropic chemical shielding and second-order quadrupolar interactions. Analysis of this spectrum yields a chemical shift anisotropy of 60(1) ppm and orientations of the chemical shift and electric field gradient tensors in the molecular frame. Experimental results are compared with those calculated usingab initioHartree–Fock and density functional theory.     

Hindered rotation and phase transition in sodium gallohydride according to the NMR data

Polycrystalline sodium gallohydrides with different hydrogen isotope compositions, NaGaH₄, NaGaH_2.56D_1.44, and NaGaD₄, were studied over the temperature range 100–375 K by the ²H, ²³Na, and ^69,71Ga NMR methods in magnetic fields of 1.4, 1.88, and 7.04 T. The data on spin-lattice deuteron relaxation T ₁(²H) were used to determine the activation energy (～35 kJ/mol) of anion rotational motions and quadrupole coupling constant (QCC) χ _Q ⁰ (²H) = 90 kHz for the rigid lattice. To within measurement errors, the activation energy and ²H QCC were independent of the isotope composition. The low-temperature ²H NMR line was a doublet with ²H QCC χ(²H) = 70 kHz. The difference between χ ₀ and χ(T) was interpreted in terms of the librational averaging of the electric field gradient (EFG) according to the Bayer equation. The frequency of librations at 113 K was estimated (31 cm^?1). The shape of the ^69,71Ga NMR line was indicative of second-order quadrupole interaction with a nonzero asymmetry parameter η of the EFG tensor. Temperature variations in the QCC and η parameter at gallium were considered using the distorted tetrahedron model. The η value changed from 0.65 to zero (axial EFG tensor symmetry characteristic of tetragonal lattices) over the temperature range 140–295 K and again increased to 0.3 at 300–365 K, which was evidence of a change in the orientation of the distorted tetrahedral anion in the lattice. Changes in the asymmetry parameter were in agreement with the phase transition in sodium gallohydride recorded as a heat capacity jump.     

NMR spin echoes and quadrupole effects in nickel single crystals

NMR spin echo measurements of naturally abundant⁶¹Ni have been performed with Néel-type nickel single crystals at 4.2 K. The NMR excitation condition could properly be chosen in order to get signals either from nuclei situated within magnetic domains or within domain walls. In both cases a quadrupole splitting of the NMR line could be observed. By applying an external magnetic field, the direction of the domain magnetization could be varied with respect to the fcc crystal lattice. From the variation of the quadrupole splitting with the crystallographic direction, the tensor of the electric field gradient (EFG) has been derived. The quadrupole splittings and the corresponding field gradients in the principal axis system of the EFG are: Δv_Q kHz, Δv_Q kHz, Δv_Q kHz, V_<111>=(6.6±0.5)·10¹⁸ V/m², V_<110>=4.6±0.5)·10¹⁸ V/m², V_<112>=(2.0±0.5)·10¹⁸ V/m².     

Al NMR studies of NpPd5Al2

We present ²⁷Al NMR studies for a single crystal of the Np-based superconductor NpPd₅Al₂. We have observed a five-line ²⁷Al NMR spectrum with a center line and four satellite lines separated by first-order nuclear quadrupole splittings. The Knight shift clearly drops below T_c. The temperature dependence of the ²⁷Al nuclear spin-lattice relaxation rate shows no coherence peak below T_c, indicating that NpPd₅Al₂ is an unconventional superconductor with an anisotropic gap. The analysis of the present NMR data provides evidence for strong-coupling d-wave superconductivity in NpPd₅Al₂.     

H and C NMR studies of molecular orientation and dynamics in liquid crystal 6BA

The dynamics and orientation of dimers accompanying the formation and destruction of hydrogen bonds in the nematic phases of 4-n-hexylbenzoic acid (6BA) were studied by ¹³C and ²H NMR. The orientational order parameter S in the nematic phase was estimated from the quadrupole splitting of the ²H NMR spectrum. The intermolecular interaction energy for the molecular order in the nematic phase decreased with increasing temperature. The flexibility of dimers due to the destruction of the hydrogen bond is closely related to a decrease in the intermolecular interaction energy. The proportion of ²H NMR spin-lattice relaxation time (T₁) to S, which reveals the coupling of the orientational fluctuations with the hydrogen bonding processes, was observed.     

Al and Si MAS NMR investigations of cordierite glass, μ- and α-cordierite

²⁷Al and ²⁹Si Magic-Angle Spinning NMR results are reported for conventionally prepared glass of cordierite stoichiometry (2MgO · 2Al₂O₃ · 5SiO₂), the metastable high-quartz solid solution (μ-cordierite) and the high-temperature polymorph of cordierite (α-cordierite). Both, ²⁷Al two-dimensional (2D) quadrupole nutation experiments and ²⁷Al satellite transition spectroscopy (SATRAS) have been applied to identify two different tetrahedrally-coordinated aluminium sites (AlO₄). SATRAS has been used to extract the quadrupole interaction parameters and their distribution, the isotropic chemical shifts and the relative populations of the different Al sites. Both, the ²⁷Al and ²⁹Si NMR results, lead to the conclusion that a perfect Si/Al disorder does not exist in these investigated cordierite samples.     

Search for a Magnetic-Field Dependence of the Interaction of the Nuclear Quadrupole Moment with the Electric-Field Gradient

It is argued that the nuclear quadrupole–electric field gradient (EFG) interaction is, in principle, dependent on the presence of a magnetic fieldB. A rough estimate of the size of this effect yields 10⁻⁴in fields up to 10 T. However, if the site symmetry of the nucleus in question includes time-reversal symmetry, the linear dependence of the EFG onBvanishes. In diamagnetic compounds, time-reversal symmetry is violated only by the presence of nuclear spins. In such compounds, the dominant dependence of the EFG onBshould be quadratic and should be described by a fourth-rank tensor. In ferro- and antiferromagnetic compounds time-reversal symmetry is strongly violated and a linear dependence of the EFG onB, described by a third-rank tensor, is expected. A search for a magnetic field dependence of the EFG was carried out by measuring the quadrupole coupling constants (QCCs) of the²⁷Al and¹⁴N nuclei in corundum and sodium nitroprusside (SNP) by pure NQR, and by NMR in fields of 6.3 and 11 T. These diamagnetic compounds were selected because previous measurements, done in different fields, yielded differing results for the QCCs. A new technique for measuring QCCs by NMR is introduced that circumvents the necessity of precisely orienting the sample crystals. For the QCCs of both the²⁷Al and¹⁴N nuclei in corundum and SNP, respectively, a precision of distinctly better than 10⁻⁴is reached. The results obtained in 0, 6.3, and 11 T fields fully agree with each other which means that, in fields up to 11 T, any possible field dependence of the QCCs is smaller than 10⁻⁴. These results confirm that in diamagnetic compounds a linear dependence of QCCs onBis largely suppressed.     

The local structure of Cs(I) and Cs(II) in a Cs2ZnCl4 single crystal studied by nuclear magnetic resonance

The rotation patterns of the ¹³³Cs (I=7/2) nuclear magnetic resonance (NMR) in a Cs₂ZnCl₄ single crystal grown by using the slow evaporation method were measured in two mutually perpendicular crystal planes. Two different groups of Cs resonances were recorded; this result points to the existence of two types of crystallographically inequivalent Cs(I) and Cs(II). The angular dependences of the NMR spectra led to different values for the quadrupole coupling constants and asymmetry parameters: e²qQ/h=148 kHz and η=0.11 for the Cs(I) ion, and e²qQ/h=274 kHz and η=0.66 for the Cs(II) ion. The EFG tensors of Cs(I) and Cs(II) are asymmetric, and the orientations of the principal axes of the EFG tensors do not coincide. Only, the principal Y-axes of the EFG tensors coincide for the Cs(I) and Cs(II) sites. The Cs(I) ion is surrounded by 11 chlorine ions, making it rather free and high in symmetry. The Cs(II) ion has only nine neighbors and seems to be more tight than the Cs(I) ion.     

Density-functional calculation of the quadrupole splitting in the <Superscript>23</Superscript>Na NMR spectrum of the ferric wheel Na@Fe<Subscript>6</Subscript>(tea)<Subscript>6</Subscript><Superscript>+</Superscript> for various broken-symmetry states of the Heisenberg spin model

The quadrupole splitting in the ²³Na nuclear magnetic resonance (NMR) spectrum of the hexanuclear ferric wheel Na@Fe₆(tea)₆ ⁺ has been computed via an evaluation of the electric-field gradient (EFG) at the Na nucleus in the framework of density-functional theory (DFT). The simulated spectrum is compared with experimental data. A total of 2⁶ = 64 Kohn-Sham determinants (a number that reduces to eight symmetry-unique determinants due to the high S₆ symmetry of the ferric wheel) with six localised high-spin Fe(III) centres (S = 5/2) could be optimised in a self-consistent manner, and the corresponding DFT energies of all of these (broken-symmetry) determinants coincide almost perfectly according to the Ising Hamiltonian solutions, especially when the energy is computed from the B3LYP functional. The EFG at the Na atom does not depend much on the specific Kohn-Sham determinant but depends on the geometry of the ferric wheel and on the basis set used in the DFT calculations (particularly with regard to the atomic functions on the Na atom).     

Hyperfine interactions measurements on 181Ta probes in HfV2Hx compounds: (0⩽x≲4)

The electric field gradient (EFG) has been measured on ¹⁸¹Ta probe sites in HfV₂H_x alloys (0?x?4) using the time differential perturbed angular correlation technique. One observes that the main component V_zz of the EFG decreases by a factor of 2 for hydrogen concentrations increasing from x = 0 to x = 4 hydrogen atoms/formula. The opposite behavior was observed on ⁵¹V by using the NMR technique. At T = 4.2 K the EFG tensor is non-axially symmetric. The observed asymmetry factor for x = 0 is η = 0.58(3) and it slightly increases to η = 0.70 for x?4. The system is orthorhombic at low temperatures for all x and the experiments suggest that hydrogen would stabilize a tetragonal phase at higher temperatures. The relaxation effects are absent for x = 0 and vanishingly small for x ? 4 but they are observed at intermediate concentrations supporting the idea of a hydrogen ordering for x = 4.     

Structural and spectroscopic characterization of the quenched hexacelsian

The hexacelsian with disorder distribution of the Si⁴⁺ and Al³⁺ is synthesized by thermally induced transformation of a Ba-LTA zeolite. The initial Ba-LTA zeolite is annealed and quenched to room temperature. The crystal structure and microstructure i.e. long-range ordering is investigated from the polycrystalline material by the Rietveld refinement procedure while short-range ordering is investigated by the ²⁹Si and ²⁷Al MAS NMR, Raman and luminescence (Eu³⁺ doped hexacelsian) spectroscopy's. The crystal structure (space group P6₃/mcm) and microstructure (size-strain analysis) results indicate disorder distribution of the Si⁴⁺ and Al³⁺. Analysis of the spectra indicates disorder distribution of the Si⁴⁺ and Al³⁺ (²⁹Si and ²⁷Al MAS NMR spectroscopy), dynamical disorder in the structure and site symmetry lowering for the Ba²⁺ site at a low temperature (Raman and luminescence spectroscopy's).     

Electric quadrupole interaction of210Po(6+) in Bi single crystal

The electric quadrupole coupling constant of the²¹⁰Po(6⁺) isomer in a Bi single crystal was measured as a function of the temperature using the time-differential perturbed angular correlations technique. The electric field gradient (EFG) for Po in Bi is found to be temperature independent in the range 77–477 K. Using a calculated value of the nuclear quadrupole moment, the magnitude of the EFG is derived, and in turn serves to re-examine the systematics of quadrupole moments of λh ₉ ^2/2 configurations in the lead region.     

27Al pulsed nuclear magnetic resonance study of CeAl2

The magnetic properties and the electronic structures of a rare-earth aluminum intermetallic compound CeAl₂ are investigated by magnetic susceptibility measurements and ²⁷Al pulsed nuclear magnetic resonance (NMR) techniques. The magnetic susceptibility is strongly temperature-dependent, following a Curie–Weiss law down to ∼12 K, and shows an antiferromagnetic transition at 4 K. The ²⁷Al NMR spectra show a typical powder pattern for a nuclear spin I of 5/2 with the second-order nuclear quadrupole interaction at high temperature and an additional large dipolar broadening between the 4f electron spins of cerium and the ²⁷Al nuclear spins at low temperature. The ²⁷Al NMR Knight shift follows the same temperature dependence as the magnetic susceptibility, suggesting that the ²⁷Al NMR Knight shift originates from the transferred hyperfine field of the Ce 4f electron spins with the hyperfine coupling constant of A = +5.7 kOe/μ_B. The spin-lattice relaxation rate 1/T₁ is roughly proportional to temperature, as with most non-magnetic metals at high temperature, and then strongly temperature-dependent, increasing rapidly with a peak near the antiferromagnetic transition temperature and decreasing at lower temperature. The temperature dependence of the Korringa ratio K, however, suggests that the antiferromagnetic spin fluctuation signature, which is an enhancement in the Korringa ratio, is washed out owing to the geometrical cancellation of Ce 4f fluctuations at the Al sites.     

<Superscript>27</Superscript>Al NMR Study of the Structure and Dynamics of Natrolite

The temperature dependences of nuclear magnetic resonance and magic angle spinning nuclear magnetic resonance spectra of ²⁷Al nuclei in natrolite (Na₂Al₂Si₃O₁₀· 2H₂O) have been studied. The influence of water molecules and sodium ions mobility on the shape of the ²⁷Al NMR spectrum and framework dynamics have been discussed The temperature dependences of the spin–lattice relaxation times T₁ of ²⁷Al nuclei in natrolite have also been studied. It has been shown that the spin–lattice relaxation of the ²⁷Al is governed by the electric quadrupole interaction with the crystal electric field gradients modulated by translational motion of H₂O molecules in the natrolite pores. The dipolar interactions with paramagnetic impurities become significant as a relaxation mechanism of the ²⁷Al nuclei only at low temperatures (<270 K).     

EPR and optical absorption studies on VO ions in KZnClSO4·3H2O single crystals—an observation of superhyperfine structure

EPR spectra of VO²⁺ ions doped in KZnClSO₄·3H₂O single crystals have been studied at different temperatures. The EPR spectrum shows a well-resolved hyperfine and superhyperfine structure patterns. The angular variation of EPR spectra reveals the presence of more than three magnetic complexes, which correspond to distinct sites of VO²⁺ ion. From the angular variation EPR data, the spin-Hamiltonian parameters are evaluated and discussed. The optical absorption spectrum studied at room temperature shows bands corresponding to C_4v symmetry. From the EPR and optical data, the molecular-orbital bonding coefficient ε² and β² are evaluated and discussed. The observed five-line superhyperfine structure has been attributed to four protons (with I=1/2) from the surrounding water molecules of one of the vanadyl sites.     

27Al NMR spectroscopy of minerals and related materials

We present a review of the applications of²⁷Al NMR methods to investigations of the structures of minerals, primarily alumino-silicates, and related synthetic compounds. Such materials are ubiquitous in the earth and other terrestrial planets. Because of their diverse structures and compositions, they also provide examples of many situations in which²⁷Al NMR spectroscopy can provide useful information. Thus, they serve well as model compounds for synthetic crystalline and amorphous materials and usefully illustrate the applications of many techniques. The advent of high-field superconducting magnets (H ₀>9 T) has made application of²⁷Al NMR to solids much more effective than it was previously, and we focus primarily on these recent applications but also discuss older, single-crystal data.²⁷Al NMR methods can be used for many purposes in investigations of solids. Here we emphasize the following. 1) Determination of the Al coordination number and the polymerization of tetrahedrally coordinated Al. 2) Determination of tetrahedral Al/octahedral Al ratios. 3) Investigation of tetrahedral Al, Si order/disorder in, especially, framework-structure alumino-silicate phases. 4) Investigation of the static structural changes and dynamical behavior of crystals undergoing structural phase transitions. 5) Investigation of the local symmetry of Al-sites through the quadrupole coupling constant and asymmetry parameter.     

Quadrupole interactions in lithium borodeuteride

Polycrystalline samples of lithium borohydride and borodeuteride, LiBH₄ and LiBD₄, are studied by ²H, ⁷Li, and ^10,11B NMR in 7.04 T and 9.35 T magnetic fields in the temperature range 116–580 K. The ^10,11B NMR line shape of the orthorhombic phase of LiBH₄ and LiBD₄ suggests that first-order quadrupole interaction takes place. The quadrupole coupling constant (QCC) χ _q and asymmetry parameter η of the electric field gradient tensor for ¹¹B are described by linear temperature dependences: χ _q (¹¹B) = 177 ? 0.24T and η = 0.043 + 0.0014T. The electric field gradient at the positions of boron nuclei is created by external charges, primarily lithium cations. In the range of 388–391 K, the ⁷Li NMR line shape reflects the coexistence of two phase modifications of LiBH₄ and LiBD₄ and the occurrence of a reversible first-order phase transition. In the temperature range of 390–530 K, the ⁷Li NMR line shape represents a first-order quadrupole perturbed spectrum with zero asymmetry parameter and a weakly temperature dependent ⁷Li QCC. The spin-lattice relaxation time and the NMR line shape of ²H are interpreted in terms of the reorientation of the BD ₄ ^? anion about their proper symmetry axes C₂ and C₃.