Modification of hyperfine field on57Fe nuclei in substituted ferrimagnetic garnets

We review the results of the NMR on⁵⁷Fe nuclei in a number of ferrimagnetic garnets Y_3−x R_xFe₅O₁₂ (R =rare earth or Bi) and Y₃Fe_5−xM_xO₁₂ (M=Al, Ga, In). For suitable concentrations of substituted ions (x∼0.1–0.4) satellite lines in the NMR spectra of both tetrahedral and octahedral Fe ions are observed. These satellites correspond to Fe ions in the vicinity of which single substitution is situated. The splitting between the satellite and the parent line has its origin in the change of the dipolar field and in the change of crystal field effects (including the transfer of electrons). While the dipolar field is easily calculated, once the magnetic moments and the geometry is known, the origin of the change of the crystal field effects is much less clear. Experimental results show that it is anisotropic and that in some cases the anisotropy may be substantial. This anisotropy is discussed within the framework of the semiempirical “independent bond” method.     

NMR spectra of57Fe in hexagonal ferrites with magnetoplumbite structure

The NMR spectra of⁵⁷Fe in domains of MFe₁₂O₁₉ (M=Ba, Sr, Pb) were measured by spin echo technique at 4.2 K. The change of the heavy ion causes frequency shifts of lines corresponding to Fe³⁺ ions in 2b and 4f₂ sites while leaving other lines essentially unchanged; the significant role of different Fe³⁺−M²⁺ bonding was found. The dipolar broadening of lines in BaFe₁₂O₁₉ caused by random and static displacement of bipyramidal Fe³⁺ ions from the mirror plane is calculated and the results are compared with the experiment.     

Investigation of domain walls in BaFe12O19 by the NMR spin echo technique

Due to the anisotropy of the hyperfine interactions and dipolar fields in hexagonal BaFe₁₂O₁₉, the nuclear magnetic resonance frequency of ⁵⁷Fe-nuclei at different positions in domain walls situated well within the bulk samples can be detected. The dependence of the enhancement factor η on the position in the wall was measured at 4.2 K and found in good agreement with the dependence expected for a 180°-Bloch-wall. For nuclei in the wall center, a nearly uniform enhancement factor of η = 6.3 × 10³ is found. There is no evidence for a broad distribution of η due to wall pinning effects.     

57Fe NMR in Y3Fe4.5Ga0.5O12 single crystal

The angular dependence of the⁵⁷Fe NMR spectra in a single crystal of Ga substituted YIG is studied with special attention paid to the satellite lines of the octahedral iron. These satellites correspond to ferric ions in the neighbourhood of which the Ga³⁺ ion is located. The anisotropy of the hyperfine field of these satellites is in accord with the prediction of the independent bond model. A simple analysis indicates that the main source of the anisotropy, besides the dipolar interaction, is the change of the supertransferred part of the hyperfine field.Dedicated to Dr. Svatopluk Krupika on the occasion of his 65th birthday.     

Anisotropy of the Hyperfine Field on 57Fe in Pure and Substituted Yttrium Iron Garnet

Using NMR, anisotropy of the hyperfine field on ⁵⁷Fe nuclei was measured in Y₃Fe₅O₁₂ with nonmagnetic, trivalent substitutions on d (Ga³⁺) and a (Y³⁺ - yttrium antisite defect) sites which are occupied by ferric ions in a pure, stoichiometric system. The measurements were performed by the spin-echo method at liquid helium temperature. Thorough analysis of the hyperfine field anisotropy on the ⁵⁷Fe nuclei in an ideal environment and in an environment where one of Fe³⁺ nearest cation neighbours is replaced by the nonmagnetic impurity is given. When the Fe³⁺ on which the NMR is measured is on the a site and the impurity is Ga³⁺(d), the results may be interpreted in terms of the superposition model. On the other hand, the results for Fe³⁺ on the d site and Y³⁺(a) are in clear disagreement with the predictions of this model. This revised version was published online in July 2006 with corrections to the Cover Date.     

On the transferred hyperfine interaction in substituted yig

NMR of⁵⁷Fe is studied in a number of (M_xY_3–x) Fe₅O₁₂ garnets for small concentrations of M (M is either trivalent RE ion –Ho 3+, Gd 3+, Nd3+, Pr 3+, La 3+ or Bi 3+ ion). Beside the main resonance lines, the satellites were observed, which correspond to those Fe, in vicinity of which the impurity M is located. After correcting for the dipolar field, the field corresponding to the change of the transferred hyperfine interaction in M³⁺–O^2–-Fe³⁺ vs. Y³⁺–O^2–-Fe³⁺ triad was deduced from the satellites splitting. The analysis of the results indicates that the observed change in the transferred hyperfine field is mainly connected with the transfer of electrons between M³⁺ and Fe³⁺ ions and not with the local deformation around the impurity.     

NMR analysis of ferromagnets: Fe oxides

A short historical review is given on internal field NMR of ferromagnets, illustrated with recent pulsed NMR spectra of the elemental ferromagnets Fe, Co and Ni and the Fe-oxides magnetite, maghemite and hematite, which, with the exception of maghemite, have resonance frequencies first reported over 45 years ago. Since the magnetic hyperfine field at the nucleus is not known a priori, the original search frequency motivations are discussed along with the mechanisms for the initially much larger than expected (～10³) NMR signals that were observed. The ⁵⁷Fe spectra of the three principal Fe-oxide ferromagnets, magnetite (Fe₃O₄), maghemite (γ-Fe₂O₃) and hematite (α-Fe₂O₃), obtained here under uniform spectroscopic conditions, are then discussed in more detail, with a focus on the influence of particle size and vacancy content on the hyperfine fields     

Spin dynamics in LiCu<Subscript>2</Subscript>O<Subscript>2</Subscript> and NaCu<Subscript>2</Subscript>O<Subscript>2</Subscript> low-dimensional helical magnets

Comprehensive NMR investigation of low-frequency spin dynamics of LiCu₂O₂ (LCO) and NaCu₂O₂ (NCO) low-dimensional helical magnets in the paramagnetic state has been carried out for the first time. Temperature dependences of the spin–lattice relaxation rate and anisotropy on various LCO/NCO nuclei have been determined at various orientations of single crystals in an external magnetic field. The spatial asymmetry of spin fluctuations in LCO multiferroic has been discovered. The quantitative analysis of the anisotropy of spin–lattice relaxation in LCO/NCO has allowed estimating the contributions of individual neighboring Cu²⁺ ions to the transferred hyperfine field on Li⁺(Na⁺) ions.     

Dipole contribution of Fe3+ ions in 12k positions to the anisotropy energy constant of the BaFe12O19 hexaferrite

The anisotropy of local fields on ⁵⁷Fe nuclei of Fe³⁺ ions located in the 12k positions of the BaFe₁₂O₁₉ ferrite is studied at low temperatures. The contributions of the anisotropy of the dipole and hyperfine fields to the anisotropy of local fields are separated. The contribution of Fe³⁺ ions in the 12k positions to the anisotropy energy constant K ₁ is calculated in the case of the interionic magnetic dipole-dipole interaction. This contribution comprises more than one-half the experimental K ₁ value.     

Hyperfine interactions in magnetoelectric hexaferrite system

Nuclear magnetic resonance (NMR) in Y-hexaferrite system (Ba_1?xSr_x)₂Zn₂Fe₁₂O₂₂ was measured on both monocrystalline and polycrystalline samples at liquid helium temperature. Corresponding ab-initio calculation of the hyperfine parameters was also performed. The signal from ⁵⁷Fe was detected in the frequency interval 65–76 MHz, while NMR spectrum of ⁶⁷Zn nuclei occurs between 15 and 30 MHz. Due to the disorder in two tetrahedral sublattices occupied partly by Zn and partly by Fe, the NMR lines are broad and the spectra are poorly resolved. Comparison between the experimentally observed ⁶⁷Zn spectra and the spectra modelled using the calculated hyperfine parameters was made. It indicates that the spectra of ⁶⁷Zn can be used to determine the distribution of Zn and Fe between the two tetrahedral sublattices.     

Mössbauer studies of the irradiation effects of Y1.6Ca1.4V0.45Sn0.5Fe4.05O12

Y_1.6Ca_1.4V_0.45Sn_0.5Fe_4.05O₁₂ has been bombarded with a 0.56 GeV C⁶⁺ ion beam. The vacancies and vacancy clusters induced by the irradiation change the directions of hyperfine fields around the defects. The reduction of the magnetic hyperfine field is caused by the lower superexchnage field due to the formation of the O^2– vacancies. The change of direction of the hyperfine field has also been observed in Mössbauer spectra. X-ray diffraction showed that the defects give rise to an increase of the lattice constant of the samples.     

Single-Ion Mechanism of Weak Ferromagnetism and a Spin-Flop Transition in One- and Two-Position Antiferromagnets

Nuclear resonance reflectivity from a [Dy₁₉Gd₁₉] × 20 superlattice has been measured utilizing the 25.652 keV nuclear level of ¹⁶¹Dy. The measured time spectra of nuclear resonance reflectivity make it possible to reveal the variation of the hyperfine magnetic field B_hf on dysprosium nuclei in the temperature range of 4–110 K and to determine the relaxation time of the hyperfine field, using the decay speed-up of the excited state of ¹⁶¹Dy nuclei.     

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.     

Bulk magnetization and 1H NMR spectra of magnetically heterogeneous model systems

Bulk magnetization and ¹H static and magic angle spinning (MAS) nuclear magnetic resonance (NMR) spectra of two magnetically heterogeneous model systems based on laponite (LAP) layered silicate or polystyrene (PS) with low and high proton concentration, respectively, and ferrimagnetic Fe₂O₃ nano- or micro-particles have been studied. In LAP+Fe₂O₃, a major contribution to the NMR signal broadening is due to the dipolar coupling between the magnetic moments of protons and magnetic particles. In PS+Fe₂O₃, due to the higher proton concentration in polystyrene and stronger proton–proton dipolar coupling, an additional broadening is observed, i.e. ¹H MAS NMR spectra of magnetically heterogeneous systems are sensitive to both proton–magnetic particles and proton–proton dipolar couplings. An increase of the volume magnetization by ～1 emu/cm³ affects the ¹H NMR signal width in a way that is similar to an increase of the proton concentration by ～2×10²²/cm³. ¹H MAS NMR spectra, along with bulk magnetization measurements, allow the accurate determination of the hydrogen concentration in magnetically heterogeneous systems.     

Asymmetric line-width effects in the presence of resolved second order splittings: the E.S.R. spectra of 1,1-difluoroalkyl radicals in fluid solutions

The solution E.S.R. spectra of radicals of the type R?F₂ exhibit marked line broadening attributable to rotational modulation of the ¹⁹F anisotropic hyperfine interactions. This dipolar broadening is restricted to lines associated with the triplet state of the two equivalent ¹⁹F nuclei and for slowly rotating radicals only the singlet state line is readily detectable.     

Carbon-13 and Fluorine-19 NMR Spectroscopy of the Supramolecular Solid p-tert-Butylcalix[4]arene ·α,α,α-trifluorotoluene

The supramolecular 1 : 1 host–guest inclusion compound, p-tert-butylcalix[4]arene ·α,α,α-trifluorotoluene, 1, is characterized by ¹⁹F and ¹³C solid-state NMR spectroscopy. Whereas the ¹³C NMR spectra are easily interpreted in the context of earlier work on similar host–guest compounds, the ¹⁹F NMR spectra of solid 1 are, initially, more difficult to understand. The ¹⁹F{¹H} NMR spectrum obtained under cross-polarization and magic-angle spinning conditions shows a single isotropic resonance with a significant spinning sideband manifold. The static ¹⁹F{¹H} CP NMR spectrum consists of a powder pattern dominated by the contributions of the anisotropic chemical shift and the homonuclear dipolar interactions. The ¹⁹F MREV-8 experiment, which minimizes the ¹⁹F–¹⁹F dipolar contribution, helps to identify the chemical shift contribution as an axial lineshape. The full static ¹⁹F{¹H} CP NMR spectrum is analysed using subspectral analysis and subsequently simulated as a function of the ¹⁹F–¹⁹F internuclear distance (D_FF = 2.25 ± 0.01 Å) of the rapidly rotating CF₃ group without including contributions from additional libration motions and the anisotropy in the scalar tensor. The shielding span is found to be 56 ppm. The width of the centerband in the ¹⁹F{¹H} sample-spinning CP NMR spectrum is very sensitive to the angle between the rotor and the magnetic field. Compound 1 is thus an attractive standard for setting the magic angle for NMR probes containing a fluorine channel with a proton-decoupling facility.     

Anomalous hyperfine field and orbital moment of cobalt in RCo2; R = Pr,Nd, Sm,Gd, Tb,Dy, Ho,Er and Tm

⁵⁹Co spin echo NMR spectra in the magnetically ordered phase of the MgCu₂ type RCo₂ compounds (R = Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er and Tm) have been observed. For the RCo₂ with the easy direction of magnetication parallel to the 〈011〉 or 〈111〉 direction, the ⁵⁹Co hyperfine fields at two magnetically inequivalent Co sites are found to be antiparallel, revealing a large anisotropy in the ⁵⁹Co hyperfine field. The results are discussed in terms of a large and anisotropic orbital moment of Co. The transferred hyperfine field due to rare earth spins is estimated from well resolved satellite lines observed in Tb_1?xY_xCo₂. The nuclear quadrupole splitting in the magnetically ordered phase is found to be always larger than that in the paramagnetic phase.     

Composition and magnetic properties of hexagonal Ca,La ferrite with magnetoplumbite structure

A polycrystalline crystal-oriented sample containing 97% of Ca_0,814²⁺La_0.341³⁺Fe_0.228²⁺Fe_11.617³⁺O₁₉ and 3% non-magnetic impurities was prepared. The magnetization and anisotropy field are very similar to those of BaFe₁₂O₁₉, except for the anisotropy field at 4K, which is lower. The value σ_s = 75.7 gausscm³g^?1 measured at 290 K is considerably higher than values reported earlier in the literature.     

The 59Co nuclear magnetic resonances in the intermetallic compounds

The anisotropic hyperfine fields of the intermetallic compounds have been studied by the spin echo method and were obtained from the NMR spectra of ⁵⁹Co nuclei in ThCo₅ and YCo₅ which have the high anisotropy fields resulting from the orbital moments. The intermetallic compounds, ThCo_5.3 and YCo_5.3, have been also investigated.     

A15N-1H dipolar CSA solid-state NMR study of polymorphous polyglycine (-CO-CD2-15NH-)n

The solid-state¹H MAS (magic-angle spinning),²H static,¹⁵N CP (cross polarization)-MAS and¹⁵N-¹H dipolar CSA (chemical shielding anisotropy) NMR (nuclear magnetic resonance) spectra of two different modifications of C_α-deuterated^l5N-polyglycine, namely PG I and PG II (-CO-CD₂-^l5NH-)_n are measured. The data from these spectra are compared to previous NMR, infrared, Raman and inelastic neutron scattering work. The deuteration of C_α eliminates the largest intramolecular¹H-¹H dipolar coupling. The effect of the remaining (N)H-(N)H interaction (～5 kHz) is not negligible compared to the¹⁵N-¹H coupling (about 10 kHz). Its effect on the dipolar CSA spectra, described as a two-spin system, is analyzed analytically and numerically and it is shown that those parts of the powder spectrum, which correspond to orientations with a strong dipolar¹⁵N-¹H interaction, can be described as an effective two-spin system, permitting the measurement of the strength of the¹⁵N-¹H dipolar interaction and the orientation of the dipolar vector with respect to the¹⁵N CSA frame. While in the PG II system the¹⁵N CSA tensor is collinear with the amide plane, in the PG I system the CSA tensor is tilted ca. 16° with respect to the (δ₁₁δ₂₂) CSA plane.