Hyperfine interactions in Sc<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Y<Subscript>x</Subscript>Fe<Subscript>2</Subscript> cubic Laves alloys

Effects of hybridization of 3d bands of iron with 3d bands of scandium and 4d bands of yttrium in Sc_1?xY_xFe₂ cubic Laves alloys (0≤_x≤1) are studied by the nuclear magnetic resonance method. The concentration dependences of the lattice parameters a, saturation magnetization σ, and hyperfine fields at the ⁵⁷Fe, ⁴⁵Sc, and ⁸⁹Y nuclei—as well as the ²⁷Al impurity nuclei, whose atoms substitute iron atoms in the lattices of these alloys—are measured. The “local” and “induced” contributions to hyperfine fields at the ⁵⁷Fe nuclei are separated and the magnetic moments at iron atoms are estimated. It is found that the hybridization effect leads to the formation of magnetic moments at Sc and Y atoms (whose direction is opposite to the direction of the magnetic moment at iron atoms) and is responsible for the ferrimagnetic structure in Sc_1?xY_xFe₂ alloys.     

Anisotropy of hyperfine field in diamagnetically substituted YIG

The results of the nuclear magnetic resonance of ⁵⁷Fe in Al-, Ga- and In-substituted Y₃Fe₅O₁₂ garnets are reported. When diamagnetic Ga³⁺ or Al³⁺ ions are substituted for tetrahedral Fe³⁺ ions, four satellite lines in the NMR spectrum of octahedral Fe³⁺ ions appear. The substitution of In³⁺ ions for octahedral Fe³⁺ ions leads to three satellite lines in the spectrum of tetrahedral Fe³⁺ ions. The hyperfine fields of these satellites are explained using the independent bond model for the hyperfine interaction. Suprisingly large change of the anisotropic part of the hyperfine field relative to the isotropic one was found.     

The temperature dependence of the hyperfine parameters of YIG below the Curie point

The temperature dependence of the hyperfine parameters of the ⁵⁷Fe nuclei in yttrium iron garnet Y₃Fe₅O₁₂ (YIG) between room temperature and the Curie point was studied by means of conventional Mößbauer transmission spectroscopy. The critical exponent β, which describes the temperature dependence of the magnetic hyperfine field of ⁵⁷Fe in YIG, was found to be 0.29(1) and 0.33(1) in the [a]- and (d)-sublattice, respectively. In the temperature region just below the Curie point relaxation of the internal hyperfine fields could be observed. The phase transition at the Curie point shows a distinct dependence on the grain size in the sample.     

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.     

Magnetic collapse in yttrium iron garnet Y<Subscript>3</Subscript>Fe<Subscript>5</Subscript>O<Subscript>12</Subscript> at high pressure

The effect of high pressures up to 70 GPa on single-and polycrystalline samples of yttrium iron garnet Y₃⁵⁷Fe₅O₁₂ is studied by Mössbauer absorption spectroscopy (for the ⁵⁷Fe nucleus) in a diamond-anvil cell. It is found that the hyperfine magnetic field H_hf at ⁵⁷Fe nuclei vanishes abruptly at a pressure of 48 ± 2 GPa, which indicates the transition of the crystal from the ferrimagnetic state to nonmagnetic one. The magnetic transition is irreversible. When the pressure decreases, the magnetic state is not recovered and the garnet remains nonmagnetic until zero pressure. The behavior of the quadrupole splitting and isomer shift shows that, simultaneously with the magnetic transition, irreversible electron and possibly spin transitions occur with changes in the local crystalline structure. The mechanisms of the magnetic collapse are discussed.     

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.     

Isotropic paramagnetic hyperfine interaction: observed at matrix isolated57Fe ions in argon

A clean paramagnetic⁵⁷Fe Mössbauer spectrum due to an isotropic hyperfine interaction was observed at “almost free” Fe atoms in a frozen argon matrix. It was obtained by ion implantation λ⁵⁷Co in an argon matrix at 4.2 K and it is due to⁵⁹Fe⁺(3d⁷) ions in a magnetically isotropic Γ₆ or Γ₇ Kramers state. The hyperfine coupling constant of the free⁵⁷Fe⁺(3d⁷) ion in the nuclear groundstate is deduced to be A=5.0(3), 7.9(5) or 11.1(6) MHz, depending whether the Fe⁺(3d⁷) is in a J=9/2, 7/2 or 5/2 state respectively.     

Specific features of magnetic states of impurity iron ions in the perovskite La<Subscript>0.75</Subscript>Sr<Subscript>0.25</Subscript>Co<Subscript>0.98</Subscript> <Superscript>57</Superscript>Fe<Subscript>0.02</Subscript>O<Subscript>3</Subscript>

Single-phase polycrystalline La_0.75Sr_0.25Co_0.98⁵⁷Fe_0.02O₃ samples have been prepared by solidstate ceramic technology. The samples have the rhombohedral structure (space group \(R\bar 3c\)). The studies of perovskite La_0.75Sr_0.25Co_0.98⁵⁷Fe_0.02O₃ by Mössbauer spectroscopy on impurity ⁵⁷Fe nuclei in the temperature range of 5–293 K have revealed the existence of a superparamagnetic relaxation in the temperature range of 100–210 K. The parameters of hyperfine interactions (hyperfine magnetic fields, line shifts, and quadrupole shifts) and the anisotropy energy have been measured, and the frequencies of magnetic moment relaxation of iron ions have been estimated.     

57Fe Mössbauer study of Li x Fe1-y Co y PO4 (y = 0, 0.1, 0.2) as cathode material for Li-ion batteries

Lithium iron phosphates LiFe_1-y Co _y PO₄ (y = 0, 0.1, 0.2) exposed to a charging process were studied by ⁵⁷Fe Mössbauer spectroscopy taking into account XRD and SEM data. Hyperfine parameters of the spectra were determined above and below the magnetic ordering temperature for all the samples. It was shown that the presence of Co impurity atoms in lithium phosphates gives no effect on the hyperfine interaction of ⁵⁷Fe²⁺ cations. However, Co atoms in the nearest cation environment of Fe atoms lead to a significant change of the hyperfine interactions of ⁵⁷Fe³⁺ cations. The Co impurity atoms distribution over the positions of the iron atoms in the structure is found not to be statistical,but correlated.     

Magnetic properties of R2Fe17−xGax (R=Y and Gd) compounds

The magnetic properties of Y₂Fe_17−xGa_x for 3≤x≤7 and Gd₂Fe_17−xGa_x for 5≤x≤7 have been investigated using ⁵⁷Fe Mössbauer spectroscopy. These compounds have the rhombohedral Th₂Zn₁₇ structure. X-ray diffraction analysis of aligned powders shows that the easy direction of magnetization is parallel to the c-axis in Y₂Fe₁₀Ga₇ and Gd₂Fe₁₀Ga₇ and is perpendicular to the c-axis in Y₂Fe₁₄Ga₃, Y₂Fe₁₂Ga₅, Gd₂Fe₁₂Ga₅ and Gd₂Fe₁₁Ga₆. Mössbauer studies indicate that those samples are ordered ferromagnetically. The ⁵⁷Fe hyperfine field decreases with increasing Ga content. This decrease results from the decreased magnetic exchange interactions resulting from Ga substitution. The average isomer shift, δ, for R₂Fe_17−xGa_x (R=Y and Gd) at room temperature is positive and the magnitude of δ increases with increasing Ga content.     

High field Mössbauer investigations of FexN (x=3,4)

⁵⁷Fe transmission Mössbauer measurements were carried out on Fe₃N and Fe₄N in applied fields up to 13.5 T to study the influence of an external field (B _a) on the hyperfine field of Fe atoms with localized and itinerant moments. These results are compared with augmented spherical wave band structure calculations.     

Electron spin relaxation studies of impurity iron ions in ferroelectric lithium niobate

The nuclear hyperfine structure of dilute impurity iron ions in ferroelectric lithium niobate is investigated via⁵⁷Fe Mössbauer effect (ME). The ME spectra exhibit typical slow electron spin relaxation effects associated with Fe³⁺ ions in the⁶S_5/2 state, which are analysed using spin-Hamiltonian formalism. For Fe³⁺ ions, the principal axis of EFG tensor is found to be parallel to the crystallographic c-axis. The strong external magnetic field of 47 KOe is used to study magnetic and crystal field effects on the ME hyperfine structure.     

Mössbauer effect studies of the Dy12Fe82B6 system

The Mössbauer measurements of both⁵⁷Fe and¹⁶¹Dy in Dy₁₂Fe₈₂B₆ system are reported. The presence of B exceeds the magnetic hyperfine fields at both⁵⁷Fe and¹⁶¹Dy nuclei as compared to corresponding pure metals Fe and Dy respectively. The only small excess of the hyperfine field at⁵⁷Fe nucleus is observed. The excess at¹⁶¹Dy nucleus is about 12% of the free ion Dy³⁺ value.     

NMR study of rapidly quenched crystalline and amorphous Fe-B alloys

Amorphous and microcrystalline Fe-B alloys (4–25 at % B) obtained by rapid quenching of the melt were studied using the pulsed nuclear magnetic resonance (NMR) of ¹¹B nuclei at 4.2 K. Alloy samples were prepared from both a natural isotope mixture and a mixture of the ⁵⁶Fe and ¹¹B isotopes. The NMR spectra were measured as a function of the boron content. The maximum hyperfine fields at the ¹¹B nuclei sites are 25–29 kOe and overlap the values of the hyperfine fields at the ¹¹B nuclei sites in the tetragonal and orthorhombic Fe₃B phases and also in the α-Fe phase containing boron as a substitutional impurity. The short-range order and local atomic structure of the amorphous Fe-B alloys were determined. The amorphous alloys are found to consist of microregions (clusters) with a short-range order similar to that in the tetragonal or orthorhombic Fe₃B phase or the α-Fe phase.     

<Superscript>57</Superscript>Fe NMR study of amorphous and rapidly quenched crystalline Fe-B alloys

Amorphous and crystalline Fe-B alloys (5–25 at % B) were studied using pulsed ⁵⁷Fe nuclear magneticr esonance at 4.2 K. The alloy samples were prepared from a mixture of the ⁵⁷Fe and ¹⁰B isotopes by rapid quenching from the melt. In the microcrystalline Fe-(5–12 at %) B alloys, the resonance frequencies were measured for local states of ⁵⁷Fe nuclei in the tetragonal and orthorhombic Fe₃B phases and also in α-Fe. The resonance frequencies characteristic of ⁵⁷Fe nuclei in α-Fe crystallites with substitutional impurity boron atoms in the nearest neighborhood were also revealed. In the resonance frequency distribution P(f) in the amorphous Fe-(18–25) at % B alloys, there are frequencies corresponding to local Fe atom states with short-range order of the tetragonal and orthorhombic Fe₃B phases. As the boron content decreases below 18 at %, the P(f) distributions are shifted to higher frequencies corresponding to ⁵⁷Fe NMR for atoms exhibiting a short-range order of the α-Fe type. The local magnetic structure of the amorphous Fe-B alloys is also considered.     

Structural and magnetic properties of iron doped YBa2Cu3O6+y and of its impurity phases: A57Fe Mössbauer study

We study the properties of Fe-doped YBa₂Cu₃O_6+y , in connection with electric field gradient and hyperfine field calculations which we have performed for high spin Fe³⁺ and Fe⁴⁺ in the two copper sites, with various oxygen environments. We also briefly describe results obtained on Fe doped Y₂BaCuO₅ and on YBaCu FeO_5+δ.     

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.     

EPR study of impurity iron ion clusters in BaF<Subscript>2</Subscript> crystals

Tetragonal paramagnetic centers with spin S = 7/2 were detected in x-ray-irradiated BaF₂: Fe (c_Fe ≈ 0.002 at. %) crystals using the EPR method. Electronic transitions between the |±1/2〉 states of a Kramers doublet were observed in the X and Q ranges. In the EPR spectra of the tetragonal centers, a ligand hyperfine structure (LHFS) was observed corresponding to the interaction of the electron magnetic moment of the tetragonal center with eight equivalent ligands. The large spin moment, significant anisotropy of the magnetic properties, and the characteristic LHFS indicate that the tetragonal center is a Fe^1.5+?Fe^1.5+ dimer in which the two iron ions are bound via superexchange interaction. It is assumed that, before crystal irradiation, this dimer was in the Fe³⁺(3d⁵)?Fe⁺(3d⁷) state.     

Hyperfine magnetic interactions of 57Fe nuclei in NaFeAs arsenide

The results of the Mössbauer effect studies of layered NaFeAs arsenide in a wide temperature range are presented. The measurements at T > T _N demonstrate that the main part (～90%) of iron atoms are in the low-spin state Fe²⁺. The other atoms can be attributed to the impurity NaFe₂As₂ phase or to the extended defects in NaFeAs. The structural phase transition (at T _S ≈ 55 K) does not produce any effect on hyperfine parameters (δ, Δ) of iron atoms. At T < T _N, the spectra exhibit the existence of a certain distribution of the hyperfine magnetic field (H _Fe) at ⁵⁷Fe nuclei, indicating the inhomogeneity of the magnetic environment around iron cations. The analysis of the temperature behavior of the distribution function p(H _Fe) allows us to determine the temperature of the magnetic phase transition (T _N = 46 ± 2 K). It has been found that the magnetic ordering in the iron sublattice has a two-dimensional type. The analysis of the H _Fe(T) dependence in the framework of the Bean-Rodbell model reveals a first-order magnetic phase transition accompanied by a drastic change in the electron contributions to the main component (V _ZZ ) and the asymmetry parameter (η) of the tensor describing the electric field gradient at ⁵⁷Fe nuclei.