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.     

Mössbauer study of the modulated magnetic structure of FeVO<Subscript>4</Subscript>

Mössbauer spectroscopy is used to study the FeVO₄ multiferroic, which undergoes two magnetic phase transitions at T _N1 ≈ 22 K and T _N2 ≈ 15 K. The first transition (T _N1) is related to transformation from a paramagnetic state into a magnetically ordered state of a spin density wave, and the second transition (T _N2) is associated with a change in the type of the spatial magnetic structure of the vanadate. The electric field gradient tensor at ⁵⁷Fe nuclei is calculated to perform a crystal-chemical identification of the partial Mössbauer spectra corresponding to various crystallographic positions of Fe³⁺ cations. The spectra measured in the range T _N2 < T < T _N1 are analyzed on the assumption about amplitude modulation of the magnetic moments of iron atoms μ_Fe. The results of model intersection of the spectra recorded at T < T _N2 point to a high degree of anharmonicity of the helicoidal magnetic structure of the vanadate and to elliptic polarization of μ_Fe. These features are characteristic of type-II multiferroics. The temperature dependences of the hyperfine interaction parameters of ⁵⁷Fe nuclei that were obtained in this work are analyzed in terms of the Weiss molecular field model on the assumption of orbital contribution to the magnetic moments of iron cations.     

Pressure-Induced Decrease in the Curie Temperature of Gd<Subscript>2</Subscript>Fe<Subscript>17</Subscript>: LSDA+U Calculations

To explain the magnetic properties of advanced ferromagnetic intermetallic compounds of the R₂Fe₁₇ (R is a rare-earth element) class, experimentalists often use the hypothesis of competition between ferromagnetic exchange and antiferromagnetic exchange between four types of the nearest iron atoms in nonequivalent lattice sites. For the rhombohedral Gd₂Fe₁₇ ferromagnet, we calculate the magnetic moments of iron and gadolinium ions, the parameters of exchange between Fe atoms, and Curie temperature T_C at a zero pressure and during hydrostatic lattice compression. The magnetic moment of the unit cell of Gd₂Fe₁₇ is shown to decrease under pressure, and this decrease is almost completely associated with a decrease in the magnetic moments of Fe rather than Gd ions, the pressure dependence of the magnetic moments of which is weaker by an order of magnitude. In contrast to the hypothesis regarding the competition of exchange interactions between different kinds of Fe atoms, the parameters of exchange between the nearest iron atoms in different crystallographic sites are found to be positive ferromagnetic (at a zero pressure and during compression), and a ferromagnetic character of interaction is shown to remain unchanged under pressure even for Fe atoms in the so-called dumbbell sites with the nearest interatomic distances. The Curie temperature T_C of Gd₂Fe₁₇ is shown to decrease with increasing pressure. The changes in the exchange parameters and the magnetic moments of Gd₂Fe₁₇ during compression are found to be mainly related to a change in the position of energy spectrum branches with respect to each other and the Fermi level ?_F rather than to a change in the overlapping of wavefunctions, which play a minor role.     

Magnetic properties of rare earth iron borates: Spectroscopic investigation by the method of rare earth probe

The magnetic phase transitions and magnetic structures in RFe₃(BO₃)₄ (R = Y, Gd-Er) iron borates have been investigated by the method of erbium spectroscopic probe. The magnetic ordering temperatures have been determined. On the basis of the comparison of the character of splitting of the spectral lines of the probe Er³⁺ ion in RFe₃(BO₃)₄(R = Y, Dy-Er) iron borates and in GdFe₃(BO₃)₄, a complicated whose magnetic structure is known, a conclusion is drawn about the orientation of the magnetic moments of iron: in dysprosium and terbium iron borates, an easy-axis magnetic structure is implemented, whereas an easy-plane structure occurs in holmium, erbium, and yttrium iron borates.     

Nitrogen-containing compounds <Emphasis Type="Italic">R</Emphasis>Fe<Subscript>11</Subscript>TiN<Subscript>x</Subscript> (<Emphasis Type="Italic">R</Emphasis> = Gd or Lu)

The structure and magnetic properties of RFe₁₁TiN compounds (R=Gd or Lu) containing nitrogen are investigated. Magnetic measurements are performed on a magnetometer in magnetic fields up to 100 kOe in the temperature range from 4.2 to 750 K with the use of RFe₁₁TiN single crystals, RFe₁₁TiN powders placed in a ceramic cell, and samples oriented in an external magnetic field. It is found that the nitridation leads to an increase in the Curie temperature and the saturation magnetization. The samples studied are uniaxial over the entire temperature range of magnetic ordering. The magnetic anisotropy decreases upon nitridation. It is demonstrated that, within the local anisotropy model, the decrease in the magnetic anisotropy constant K₁ can be explained by the redistribution of the electron density in the vicinity of the crystallographic positions occupied by iron atoms.     

Electronic and magnetic properties of Fe<Subscript>2</Subscript>SiC

The electronic structure and magnetic properties of Fe₂SiC compound have been studiedusing the framework of an all-electron full-potential linearized augmented-plane wave(FP-LAPW) method within the local density (LSDA) and + U corrected(LSDA + U)approximations. An antiferromagnetic spin ordering of Fe atoms is shown to be the groundstate for this compound. From the electronic band structures and density of states (DOS),Fe₂SiC has ametallic character and from the analysis of the site and momentum projected densities, itis deduced that the bonding is achieved through hybridization of Fe-3d with C-2p states andFe-3d withSi-3pstates. It is also pointed out that the Fe-C bonding is more covalent than Fe-Si. In theFM phase, the spin polarized calculations indicate that the total magnetic moment ofFe₂SiC increasesfrom 0.41 to 4.33μ _B when the Hubbard U parameter for iron isconsidered.     

Effect of the Composition and the Crystal Structure on the Electrophysical Properties of the Ni<Subscript>1–<Emphasis Type="Italic">x</Emphasis></Subscript>W<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> System at Low Temperatures

The problem of establishing the correlation between, on the one hand, the chemical and phase compositions of Ni_1–xW_x alloys (0 ≤ x ≤ 0.5) and, on the other hand, the character of the temperature dependences of the electrical resistivity, is considered. Based on the experimental ρ(T) curves, the concentration dependences of are reconstructed in the wide temperature range (50 K ≤ T ≤ 273 K). The ρ(x) curves have features related to a change in the crystal structures of the alloys (concentration fcc–bcc phase transition), their magnetic structures and percolation processes occurring in the two-phase fcc + bcc medium.     

High-temperature redistribution of cation vacancies and irreversible magnetic transitions in the Fe<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>S nanodisks observed by the Mössbauer spectroscopy and magnetic measurements

The hexagonal pyrrhotite Fe_1?x S nanodisks with the NiAs-type structure were synthesized by thermal decomposition of ferrous chloride and thiourea in oleylamine. The Mössbauer spectroscopy and magnetic measurements data indicate that a mixture of antiferromagnetic (AFM) and ferrimagnetic (FRM) phases with the NC (N ≥ 3) and 2C-type superstructures is present in the Fe_1?x S compound at temperatures between 80 K and Néel temperature T _N. At T < 370 K, the AFM phase prevails over the FRM phase. At T > 370 K, a redistribution of iron vacancies takes place, and the vacancy ordering transforms from the NC (N ≥ 3) to 2C-type which essentially increases the magnetization with maximum value at 470 K. Heating the sample above the Néel temperature 565 K leads to a random distribution of vacancies, and this state is quenched upon subsequent cooling of the sample to 300 K. This gives rise to a pure AFM structure with a zero magnetic moment due to a total compensation of the moments in neighboring iron layers. Thus, the high-temperature redistribution of cation vacancies leads to irreversible magnetic transformations in the Fe_1?x S nanoparticles.     

X-ray and Mössbauer studies of the Tb<Subscript>0.3</Subscript>Dy<Subscript>0.7</Subscript>Fe<Subscript>2 − <Emphasis Type="Italic">x</Emphasis></Subscript>Co<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> system alloys

A complex study of the phase composition, atomic and crystalline structure, magnetic properties, and superfine interactions of the Tb_0.3Dy_0.7Fe_{2 ? x} Co _x system alloys (x = 0?1.3) has been performed. The synthesized alloys are isotypic with the cubic Laves phase (C15 type), their cell parameter monotonically decreases with an increase in the Co content and, hence, the saturation magnetostriction also does. However, the concentration dependences of the Curie temperature, saturation magnetization, and superfine magnetic field strength measured in the Mössbauer experiment display a nonmonotonic (dome-like) character.     

Magnetic properties of Fe<Subscript>3</Subscript>C ferromagnetic nanoparticles encapsulated in carbon nanotubes

The low-temperature dependences of magnetic characteristics (namely, the coercive force H _c , the remanent magnetization M _r , local magnetic anisotropy fields H _a, and the saturation magnetization M _s ) determined from the irreversible and reversible parts of the magnetization curves for Fe₃C ferromagnetic nanoparticles encapsulated in carbon nanotubes are investigated experimentally. The behavior of the temperature dependences of the coercive force H _c (T) and the remanent magnetization M _r (T) indicates a single-domain structure of the particles under study and makes it possible to estimate their blocking temperature T _B = 420–450 K. It is found that the saturation magnetization M _s and the local magnetic anisotropy field H _a vary with temperature as ～T ^5/2.     

Investigation of the cation distribution in perovskite-like oxides with Mössbauer spectroscopy

Complex perovskite-like oxides, such as LnFe_2/3Mo_1/3O₃ orthoferrites, Ln_8?ySr_yCu_8?xFe_xO₂₀ (8-8-20), Pr₄BaCu₄FeO_13-δ(4-1-5), YBa_2-yLa _y Cu_3-xFe _x O_7-δ and Y_1-yCa _y Ba _y La _y Cu_3-xFe _x O_7-δ (1-2-3), are studied by means of Mössbauer spectroscopy. At room temperature, the spectra of the orthoferrites contain only magnetic components. The spectra of the 1-2-3 compounds contain only magnetically disordered components: iron atoms substitute for copper at Cu(1) sites, taking various configurations: planar squares, quadratic pyramids, and octahedra. Cuprates 8-8-20 and 4-1-5 have a wide diversity of spectra. In the 8-8-20 oxides, a phase related to the pyramidal environment of the iron cations is present at any iron concentration. In all the perovskites, iron cations become magnetically ordered only at octahedral sites of the structure.     

Specific features of the structure,magnetic properties,and heat capacity of intercalated compounds Cr<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>TiSe<Subscript>2</Subscript>

Structural features, magnetic properties, and heat capacity of Cr _x TiSe₂ intercalated compounds with a layered structure have been studied experimentally for 0 ≤ x ≤ 0.5. It is shown that, at high chromium concentrations (x > 0.25), the magnetic properties of the compounds are strongly affected by the degree of ordering and distribution pattern of the intercalated atoms. Depending on the cooling rate of samples of the same composition (x = 0.5), an antiferromagnetic or a cluster-glass-type state can be obtained. Heat capacity measurements have revealed a nonmonotonic variation in the lattice rigidity with increasing concentration of intercalated atoms.     

Magnetic and thermal properties of single-crystal NdFe<Subscript>3</Subscript>(BO<Subscript>3</Subscript>)<Subscript>4</Subscript>

The neodymium ferroborate NdFe₃(BO₃)₄ undergoes an antiferromagnetic transition at T _N = 30 K, which manifests itself as a λ-type anomaly in the temperature dependence of the specific heat C and as inflection points in the temperature dependences of the magnetic susceptibility χ measured at various directions of an applied magnetic field with respect to the crystallographic axes of the sample. Magnetic ordering occurs only in the subsystem of Fe³⁺ ions, whereas the subsystem of Nd³⁺ ions remains polarized by the magnetic field of the iron subsystem. A change in the population of the levels of the ground Kramers doublet of neodymium ions manifests itself as Schottky-type anomalies in the C(T) and χ(T) dependences at low temperatures. At low temperatures, the magnetic properties of single-crystal NdFe₃(BO₃)₄ are substantially anisotropic, which is determined by the anisotropic contribution of the rare-earth subsystem to the magnetization. The experimental data obtained are used to propose a model for the magnetic structure of NdFe₃(BO₃)₄.     

Relaxation processes in an alternating-current electric field and energy loss mechanisms in hafnium diselenide cointercalated with copper and silver atoms

Samples based on hafnium diselenide intercalated with atoms of two types, Cu_xAg_yHfSe₂ at (x + y) ≤ 0.2, have been synthesized for the first time. The frequency dependences of the components of the complex impedance have been measured using impedance spectroscopy in the frequency range from 1 Hz to 10 MHz, and the specific features of the relaxation processes occurring in samples of different compositions have been analyzed. It has been shown that the characteristic times of these processes depend not only on the total concentration of intercalated atoms, but also on the ratio between them. As the total concentration of copper and silver increases, the onset of frequency dispersion of the complex admittance shifts to the higher frequency range. The relative contributions from the conduction and relaxation polarization losses also change depending on the total and element concentrations of the intercalated atoms.     

Simulation of the structural,electronic, and magnetic properties of Fe<Subscript>3</Subscript>C<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>B<Subscript>x</Subscript> borocementites

The structural, electronic, and magnetic properties and the enthalpy of formation of iron borocementites Fe₃C_1?x B_x (x= 0, 0.25, 0.50, 0.75, 1.00) are analyzed using ab initio calculations in the framework of the electron density functional theory. It is found that the unit cell parameter a of the orthorhombic lattice increases linearly and the parameters b and c decrease as the boron concentration increases. The density of states at the Fermi level changes only slightly, and the main variations in the band structure occur in the region of the bottom of the valence bands. The magnetic moment of the iron atoms and the total magnetization and stability of the Fe₃C_1?x B_x phases increase linearly with an increase in the boron concentration.     

Phase transitions in titanium diselenide intercalated with cobaltocene at high pressures of up to 20 GPa

The pressure dependences of the kinetic properties of TiSe₂ intercalated with cobaltocene (biscyclopentadienyl-cobalt, CoCp ₂) and cobaltocene itself were measured. Anomalies are revealed in the pressure dependences of the resistance and thermopower (for the intercalated material), which are interpreted as pressure-induced structural phase transitions. The main effect of pressure on the molecules of cobaltocene as an individual compound and in the intercalated state is suppression of the intramolecular motion in the form of rotation of the cyclopentadienyl rings. The general character of the pressure effect on the kinetic properties of (CoCp ₂) _x TiSe₂ agrees well with the assumption that the bonding of the organic molecules to the host lattice is covalent.     

Magnetic and magnetoresistive properties of Gd<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Mn<Subscript>1–<Emphasis Type="Italic">x</Emphasis></Subscript>Se selenides

Gd _x Mn_1–x Se (0 ≤ х ≤ 0.15) solid solutions are synthesized on the basis of manganese monoselenide. Their magnetic and electrical properties are studied in the temperature range of 80–900 K in magnetic fields up to 10 kOe. An FCC lattice with the Fm3m space group and antiferromagnetic ordering of the magnetic moments of manganese ions is found. A monotonic reduction in the Néel temperature and an increase in the effective magnetic moment along with the gadolinium concentration are observed. Anomalies in the temperature dependence of electrical resistivity and a shift in the temperatures of anomalies in a magnetic field are found.     

Spin reorientation effects in GdFe<Subscript>3</Subscript>(BO<Subscript>3</Subscript>)<Subscript>4</Subscript> induced by applied field and temperature

Magnetic properties of GdFe₃(BO₃)₄ single crystals were investigated by ⁵⁷Fe-Mössbauer spectroscopy and static magnetic measurements. In the ground state, the GdFe₃(BO₃)₄ crystal is an easy-axis compensated antiferromagnet, but the easy axis of iron moments does not coincide with the crystal C₃ axis, deviating from it by about 20°. The spontaneous and field-induced spin reorientation effects were observed and studied in detail. The specific directions of iron magnetic moments were determined for different temperatures and applied fields. Large values of the angle between the Fe³⁺ magnetic moments and the C₃ axis in the easy-axis phase and between Fe³⁺ moments and the a₂ axis in the easy-plane phase reveal the tilted antiferromagnetic structure.     

Effect of doping by boron,carbon, and nitrogen atoms on the magnetic and photocatalytic properties of anatase

The effect of doping of titanium dioxide with the anatase structure by boron, carbon, and nitrogen atoms on the magnetic and optical properties and the electronic spectrum of this compound has been investigated using the ab initio tight-binding linear muffin-tin orbital (TB-LMTO) band-structure method in the local spin density approximation explicitly including Coulomb correlations (LSDA + U) in combination with the semiempirical extended Hückel theory (EHT) method. The LSDA + U calculations of the electronic structure, the imaginary part of the dielectric function, the total magnetic moments, and the magnetic moments at the impurity atoms have been carried out. The diagrams of the molecular orbitals of the clusters Ti₃ X (X = B, C, N) have been calculated and the pseudo-space images of the molecular orbitals of the clusters have been constructed. The effect of doping on the nature and origin of photocatalytic activity in the visible spectral range and the specific features of the generation of ferromagnetic interactions in doped anatase have been discussed based on the analysis of the obtained data. It has been shown that, in the sequence TiO_{2 ? y} N _y → TiO_{2 ? y} C _y → TiO_{2 ? y} B _y (y = 1/16), the photocatalytic activity can increase with the generation of electronic excitations with the participation of impurity bands. The calculated magnetic moments for boron and nitrogen atoms are equal to 1 μ_B, whereas the impurity carbon atoms are nonmagnetic.     

Hierarchy of percolation thresholds and the mechanism for reduction of magnetic moments of transition metals intercalated into TiSe<Subscript>2</Subscript>

The concentration dependences of the effective magnetic moment of transition metal atoms intercalated into TiSe₂ are analyzed in the framework of the percolation theory. It is shown that, depending on the degree of localization of impurity states, the effective magnetic moment is determined by the overlap of 3d orbitals of transition metals or orbitals of titanium atoms coordinated by impurity atoms.