Low-temperature magnetic behavior of the rare-earth cobaltites GdCoO<Subscript>3</Subscript> and SmCoO<Subscript>3</Subscript>

The temperature and magnetic field dependences of the static magnetization of the polycrystalline rare-earth cobaltites GdCoO₃ and SmCoO₃ have been measured. It is shown that, below room temperature, the magnetization of both compounds derives primarily from the rare-earth ion paramagnetism. The GdCoO₃ and SmCoO₃ compounds have been found to differ substantially in magnetic behavior, which can be traced to differences in their electronic shell structures. The magnetic behavior of GdCoO₃ is close to that of an array of free Gd³⁺ ions, whereas in SmCoO₃ the deviation from the free-ion properties is very large because of the Sm³⁺ ground state being crystal-field split. Van Vleck magnetic susceptibility measurements of SmCoO₃ suggest that the splitting is ～10 K.     

Temperature dependence of the spin state of a Co3+ Ion in RCoO3 (R = La,Gd) cobaltites

Changes in the spin state of Co³⁺ ions in LaCoO₃ and GdCoO₃ compounds are studied through the use of the temperature dependence of the magnetic susceptibility and the modified crystal field theory. It is shown that the spin subsystem of Co³⁺ ions in LaCoO₃ and GdCoO₃ undergoes the spin-crossover type transition between the high-spin (S = 2) and low-spin (S = 0) states without any contribution of the intermediate-spin state (S = 1).     

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.     

Effect of strontium and barium doping on the magnetic state and electrical conductivity of GdCoO3

A coordinated investigation of the magnetic and electrical properties of polycrystalline cobalt oxide compounds CdCoO₃, Gd_0.9Ba_0.1CoO₃, and Gd_0.9Sr_0.1CoO₃ is carried out. Undoped GdCoO₃ reveals a low conductivity; a magnetic moment of 7.4 μ_B per molecule, which is less than the theoretical value for the Gd³⁺ ion; and an asymptotic Curie temperature of ?6 K. Doping GdCoO₃ with barium and strontium to substitution of 10 at. % Gd brings about an increase in the conductivity and magnetic transitions at T = 300 K for Gd_0.9Ba_0.1CoO₃ and T = 170 K for Gd_0.9Sr_0.1CoO₃. The magnetization anomalies imply the formation of magnetic clusters. The behavior of the electrical conductivity at high temperatures suggests a variable activation energy. At low temperatures, Mott hopping conduction sets in.     

Magnetization studies of TbFeO3

The spontaneous magnetization and principal magnetic susceptibilities of TbFeO₃ were measured from 4.2 to 300 K. The weak ferromagnetic moment is along the c crystallographic axis in the entire temperature range. The field dependence of the magnetization at 4.2 K was also studied. The magnetic behavior is interpreted in terms of an interaction between the ordered Fe³⁺ spin system and the electrons occupying the lowest lying “accidental” doublet of the Tb³⁺ ions. The FeTb interaction and the Tb³⁺ Van Vl eck susceptibility along the c axis play significant roles in determining the magnetic configuration of the Fe³⁺ spin system. No indication was found that the TbTb interaction plays a significant role in the magnetic behavior of TbFeO₃ at temperature above 4.2 K.     

Delocalization of the Ce 4f shell in amorphous Ce75.5Co24.5

The amorphous alloy Ce_75.5Co_24.5 prepared by melt spinning has been studied through measurements of the magnetic susceptibility, magnetization, electrical resistivity, thermoelectric power and specific heat. The results are interpreted in terms of a homogeneous intermediate valence state of the Ce ions. This is inferred from a temperature-independent magnetic susceptibility at low temperature and the absence of magnetic ordering, a large linear term in the specific heat, and aT ² dependence of the electrical resistivity at low temperature followed by a steep increase with temperature up to 50 K. At this temperature, the thermoelectric power displays a maximum. The intrinsic properties are partially obscured at low temperatures by a contribution from roughly a few percent of magnetic impurities, presumably Ce³⁺ ions. They manifest themselves by an increase of the susceptibility towards low temperatures and by a broad Schottky-like contribution to the specific heat resulting from the excitation of magnetic clusters.Dedicated to Prof. Dr. S. Methfessel on the occasion of his 60th birthday     

Electronic structure,magnetic properties,and mechanism of the insulator–metal transition in LaCoO<Subscript>3</Subscript> taking into account strong electron correlations

The electronic structure of LaCoO₃ at finite temperatures is calculated using the LDA+GTB method taking into account strong electron correlations and possible spin crossover upon an increase in temperature. Gap states revealed in the energy spectrum of LaCoO₃ reduce the dielectric gap width upon heating; this allowed us to describe the insulator-metal transition observed in this compound at T = 500–600 K. The temperature dependence of the magnetic susceptibility with a peak at T ≈ 100 K is explained by the Curie contribution from thermally excited energy levels of the Co³⁺ ion. At high temperatures, the Pauli contribution from a band electron is added and the total magnetization of LaCoO₃ is considered as the sum M _tot = M _loc + M _band. The second term describes the band contribution appearing as a result of the insulator-metal transition and facilitating the emergence of a high-temperature anomaly in the magnetic susceptibility of LaCoO₃.     

Photomagnetic effect in molecular magnets based on nitrosyl complexes of ruthenium and rare-earth ions

The magnetic properties of new bifunctional molecular magnets based on nitrosyl complexes of ruthenium and thiacalix[4]arenes of rare-earth ions (Gd³⁺, Dy³⁺) have been investigated. A photoinduced decrease in the magnetization of the molecular magnet with rare-earth ions Gd³⁺ and the absence of a photomagnetic effect in crystals with rare-earth ions Dy³⁺ have been revealed at a temperature of 2 K. It has been found that, in the sample containing Dy³⁺ ions, the magnetization deviates by 6% from the calculated value for noninteracting ions. A comparison of the results obtained for two groups of isostructural samples, which differ only in the type of rare-earth ions, has demonstrated that the observed deviation of the magnetization is caused by the interaction of the orbital moment of the Dy³⁺ ions with the crystal field.     

Magnetization measurements on some rare-earth iron garnets

The magnetic properties of Fe-based singlecrystal garnets have been studied. A magnetic field up to 55 kOe in the temperature range from 4.5 to 300 K has been used. The compensation temperature (T _comp) of the studied garnets has been determined. The compensation temperature increases with the increase of the rare-earth ions (Ho³⁺ or Gd³⁺) substituting Y³⁺ ions in thec sublattice of R₃Fe₅O₁₂. AboveT _comp, the magnetization was found to be linearly field dependent. The results are in good agreement with magnetization measurements performed on polycrystaline samples, and with calculations based on the crystal field parameters of the isostructural Holmium Gallium Garnet (HoGG).     

Causes of the Metamagnetism in a Disordered EuMn<Subscript>0.5</Subscript>Co<Subscript>0.5</Subscript>O<Subscript>3</Subscript> Perovskite

The magnetic properties of the EuMn_0.5Co_0.5O₃ perovskite synthesized under various conditions are studied in fields up to 140 kOe. The sample synthesized at T = 1500°C is shown to exhibit a metamagnetic phase transition, which is irreversible below T = 40 K, and the sample synthesized at T = 1200°C demonstrates the field dependence of magnetization that is typical of a ferromagnet. Both samples have T_C = 123 K and approximately the same magnetization in high magnetic fields. The metamagnetism is assumed to be related to a transition from a noncollinear ferromagnetic phase to a collinear phase, and the presence of clusters with ordered Co²⁺ and Mn⁴⁺ ions leads to ferromagnetism. The noncollinear phase is formed due to the competition between positive Co²⁺–Mn⁴⁺ and negative Mn⁴⁺–Mn⁴⁺ and Co²⁺–Co²⁺ interactions, which make almost the same contributions, and to the existence of a high magnetic anisotropy.     

Mictomagnetic State in an EuBaCo<Subscript>2–<Emphasis Type="Italic">x</Emphasis></Subscript>O<Subscript>5.5–δ</Subscript> Single Crystal

The magnetic properties of an EuBaCo_1.9O_5.36 single crystal are studied in the temperature range T = 2–300 K and the magnetic field range H ≤ 90 kOe. This binary layered cobaltite single crystal has vacancies in the cobalt and oxygen sublattices, in contrast to the stoichiometric EuBaCo₂O_5.5 composition. All cobalt ions in EuBaCo1.9O5.36 are in a trivalent state. The single crystal has an orthorhombic structure with space group Pmmm, and its unit cell parameters are a = 3.883 Å, b = 7.833 Å, and c = 7.551 Å. The field and temperature dependences of the magnetization of the single crystal demonstrate that it is ferrimagnet below T_C = 242 K. At T < 300 K, all three spin states of the Co³⁺ ions are present. The nearest-neighbor interactions give antiferromagnetic (AFM) and ferromagnetic (FM) contributions to the exchange energy. The ratio of the AFM to the FM contributions changes when temperature decreases because of a change in the spin state of the Co³⁺ ions. The single crystal exhibits signs of mictomagnetism at low temperatures in high magnetic fields. At T = 2 K and H = 90 kOe, the zero-field and nonzero-field magnetizations are strongly different because of a uniaxial magnetic anisotropy, which tends to set magnetization along the magnetic field applied in cooling throughout the crystal volume. As a result, a complex ferrimagnetic structure with a noncollinear direction of Co³⁺ spins appears. The following phenomena characteristic of mictomagnets are also observed in the EuBaCo_1.9O_5.36 single crystal: a shift in a magnetization hysteresis loop when temperature decreases, retained hysteretic phenomena and no magnetization saturation in high magnetic fields, and an orientation transition. The mictomagnetic state in EuBaCo_1.9O_5.36 is shown to be caused by the structural distortions induced by vacancies in the cobalt and oxygen sublattices and by the frustration of AFM and FM exchange interactions.     

Faraday rotation in single crystal erbium iron garnet

Measurements of the Faraday rotation of ErIG, Er₃Fe₅O₁₂, have been performed in the 4.2–300 K temperature range in magnetic field up to 20 kOe applied along the [111] direction and at 1.15 μm wavelength. The results are analysed under the assumption that the contribution of the Fe³⁺ ions to the total Faraday rotation is the same as that of YIG, Y₃Fe₅O₁₂. The temperature and field dependences of the contribution of the Er³⁺ ions are deduced. Both magnetic and electric dipole contributions of the Er³⁺ ions are calculated; the electric dipole coefficient C_e is found to present a linear temperature dependence between 30–300 K. The temperature dependence of the Faraday rotation susceptibility differs strongly from that of the magnetic susceptibility.     

Specific heat of YFe3(BO3)4, Y0.5Gd0.5Fe3(BO3)4, and GdFe3(BO3)4

The specific heat was measured in the range 0.4–300 K in YFe₃(BO₃)₄, Y_0.5Gd_0.5Fe₃(BO₃)₄, and GdFe₃(BO₃)₄ single crystals. Sharp anomalies were found at temperatures of first-order structural, second-order antiferromagnetic, and first-order spin-reorientational transitions. A Néel temperature of about 37 K was found to be virtually independent of presence of rare-earth ions, indicating rather weak coupling of Gd and Fe subsystems. The contribution of the magnetic system to specific heat was separated through the scaling procedure allowing determination of the magnetic entropy of Fe and Gd subsystems. At the lowest temperatures, the specific heat in GdFe₃(BO₃)₄ exhibits a Schottky-type anomaly, which is due to Gd³⁺ eightfold degenerate ground-level splitting by the internal magnetic field of the Fe subsystem of about 7 T. The text was submitted by the authors in English.     

Temperature and field dependent electronic structure and magnetic properties of LaCoO3 and GdCoO3

The transformation of the band structure of LaCoO₃ in the applied magnetic field has been theoretically studied. If the field is below its critical value B_C≈65 T, the dielectric band gap decreases with the field, thus giving rise to negative magnetoresistance that is highest at T≈300÷500 K. The critical field is related to the crossover between the low- and high-spin terms of Co³⁺ ions. The spin crossover results in an insulator–metal transition induced by an increase in the magnetic field. Similar calculations have been done for GdCoO₃ which is characterized by large spin gap∼2000 K.     

Investigation of spin transition in GdCoO3 by measuring the electric field gradient at Co sites

In the present work, the time differential perturbed angular correlation (PAC) technique was used to study the temperature dependence of electric field gradient (efg) in GdCoO₃ perovskite using ¹¹¹Cd and ¹⁸¹Ta nuclear probes. The radioactive parent nuclei ¹¹¹In and ¹⁸¹Hf were introduced in the oxide lattice through chemical process during sample preparation and were found to occupy only the Co sites in GdCoO₃. The efg's at ¹¹¹Cd and ¹⁸¹Ta show temperature dependence with two different fractions each that change with temperature. In the case of ¹¹¹Cd the quadrupole frequency slowly decreases, with corresponding increase of the temperature and shows a peak like structure at around 200 K and a discontinuity at 700 K. These changes have been interpreted as thermally activated spin-state transitions from low-spin ground state configuration to the intermediate-spin state and from intermediate-spin to high-spin state of Co³⁺${\mathrm{Co}}^{3+}$ ion similar to LaCoO₃ compound. Indication of a Jahn–Teller distortion, which stabilizes the intermediate-spin state with orbital ordering, is also pointed out.     

Sur l'evolution des proprietes physiques de la perovskite GdCoO3 entre 77 et 1200 K

GdCoO₃, which has the GdFeO₃ structure, has been studied between 77 and 1200 K by D.T.A., X-ray diffraction, magnetic susceptibility, electric conductivity and thermoelectric power. All properties observed, although different from those of LaCoO₃, fit with the corresponding Goodenough localized electron model. With rising temperature cobalt ions pass progressively from a low-spin Co^III(t⁶_2ge_g⁰) state to a Co³⁺(t⁴_2ge_g²) high-spin state.     

Mössbauer effect study of Ni1−xCuxMnyFe2−yO4 system

The Mössbauer effect technique has been employed for the study of magnetic properties of spinel series Ni_1?xCu_xMn_yFe_2?yO₄ with 0.0≤x≤1.0, and y=0.6. The substitution of Mn³⁺ and Cu²⁺ ions results in a slight decrease of the hyperfine field at B‐ as well as A‐sites. The area ratio of Fe³⁺ ions at the A‐ and B‐site at 77 K indicates that Cu²⁺, Ni²⁺ and Mn³⁺ ions occupy the octahedral sites in an evidence for complete inverse spinel in this system. The temperature dependence of the hyperfine parameters has been studied for composition with x=0.5 where Nèel point T_N and Debye temperature θ_D are found to be 650 and 679 K, respectively. The temperature dependence of the sublattice magnetization σ(T) obeys a one‐third‐power law in the range 0.5N<0.99.     

Possible observation of the coexistence of superconductivity and long-range magnetic order in NdRh4B4

The ternary rare earth compound NdRh₄B₄ has been studied by means of critical field, low temperature heat capacity, and static magnetic susceptibility measurements. Features in the upper critical field and heat capacity data at 1.31 K and 0.89 K suggest the occurrence of long-range magnetic order in the superconducting state. The temperature dependence of the static magnetic susceptibility follows a Curie-Weiss law with an effective magnetic moment μ_eff = 3.58 ± 0.05 μ_B and a Curie-Weiss temperature θ_p = ?6.2 ± 1.0 K between 20 K and room temperature. However,, magnetization vs. applied magnetic field isotherms suggest the development of a ferromagnetic component in the Nd³⁺ magnetization at low temperatures.     

Separation of the contributions to the magnetization of Tm1 − x Yb x B12 solid solutions in steady and pulsed magnetic fields

The magnetization of substitutional Tm_{1 ? x} Yb _x B₁₂ solid solutions is studied in the composition range 0 < x ≤ 0.81. The measurements are performed at low temperatures (1.9–300 K) in steady (up to 11 T) and pulsed (up to 50 T, pulse duration of 20–100 ms) magnetic fields. An analysis of the experimental data allowed the contributions to the magnetization of the paramagnetic phase of the Tm_{1 ? x} Yb _x B₁₂ compounds to be separated. These contributions include a Pauli component, which corresponds to the response of the heavy-fermion manybody states that appears in the energy gap in the vicinity of the Fermi level (density of states (3?4) × 10²¹ cm^?3 meV^?1), and a contribution with saturation in high magnetic fields attributed to the localized magnetic moments ((0.8–3.7)μ_B per unit cell) of the nanoclusters formed by rare-earth ions with an antiferromagnetic interaction.     

Crystal field effect on the magnetic moment's direction of rare earth ions with low point symmetry in r4co3 (r = Tb, Ho, Dy, Er, Tm) compounds

Neutron diffraction measurements, made on powder samples, show that Ho₄Co₃ and Er₄Co₃ intermetallic compounds are ferrimagnetic at 4.2 K. The magnetic moments of the 2 holmium sites are 8.7 and 2.1 μ_B and those of the erbium sites are equal to 8.7 and 8.1μ_B. The cobal⁺ magnetic moment is 0.2μ_B for both compounds. The easy magnetization direction lies on the hexagonal plane for Ho₄Co₃ while for Er₄Co₃ there are 2 anisotropy directions. Exchange interactions between rare-earth ions of both sites are very weak compared with the total crystal field splitting of the ground state multiplet J. The crystal field parameters are calculated and the magnitude and direction of the rare-earth magnetic moments in each site is determined.