Magnetic phase diagram of a random mixture of Jahn-Teller ions

A magnetic model of a random mixture containing Jahn-Teller ions, in which several kinds of exchange interactions between the Jahn-Teller ions and between the Jahn-Teller and non-Jahn-Teller ions are assumed, is proposed and studied by using the distribution function method. It is shown that a spin glass phase occurs when these exchange interactions have different signs. Our model would be applicable to a mixture Rb₂Cr_xMn_1-xCl₄ in which the spin glass phase has been observed.     

Features of the Jahn-Teller transition in Ni1 − x Co x Cr2O4 solid solutions

The structure of Ni_{1 ? x} Co _x Cr₂O₄ solid solutions has been investigated by synchrotron X-ray powder diffraction in the temperature range of 90–350 K for compositions x = 0, 0.005, 0.01, 0.015, 0.02, 0.1, 0.5, and 0.8, and their structures have been refined using the Rietveld analysis. The T-x phase diagram for solid solutions in the studied range of temperatures and concentrations has been constructed based on the obtained data. The revealed structural phase transitions have been explained from the viewpoint of the crystal field theory and the Jahn-Teller cooperative effect. Distortions of polyhedra, which are the cause of the structural phase transition, have been evaluated. The applicability of the Landau phenomenological theory and the possibility of using the magnitude of spontaneous strains as the order parameter have been discussed.     

Jahn-Teller-type phase transitions in oxide ceramics and other solids with Cu(II) — from the viewpoint of a solid state chemist

After a short outline of the vibronic features of the local Jahn-Teller effect (E _g ? ε _g coupling) the cooperative aspects — in particular the various order patterns of the elongated octahedra in Cu(II) solids — are reviewed. While the elastic interactions can be described by energy terms of Q_ε symmetry, the local Jahn-Teller effect has Q_θ symmetry (? = 0). Phase transitions in dependence on the Cu(II) concentration are analysed in detail for oxidic ordered perovskites Ba(Sr)₂Zn(Ni)_1-x Cu_xW(Te)O₆, which exhibit ferrodistortive order patterns connected with first order phase transitions at high x-values. At lower x-values at the short-range order scale elastic Q_ε-type strains prevail as in the cases of antiferrodistortive order, leading to continuous phase transitions. Here, the cluster distribution has been successfully analysed by EPR spectroscopy.     

Mössbauer studies on cation distribution and lattice distortion in magnesium manganites

Mössbauer studies are reported on a magnesium manganite series Mg_xMn_2.9?xFe_0.1O₄ for 0.5 ? x ? 2.4. In the region x ? 1.4 two quadrupole doublets are observed while for x ? 1.8 only one doublet could be observed. Quadrupole splitting (QS) has been studied as a function of x and an unusually large QS for the outer doublet has been attributed to Jahn-Teller distortion whose onset has been located in the region 1.8 > x > 1.4; this is corroborated by X-ray diffraction studies. Probable cation distributions are proposed. Oxygen ion parameters are estimated for the compositions corresponding to x = 1 (tetragonal phase) and x = 2 (cubic phase) under point charge approximation for electric field gradient at Fe³⁺ sites.     

Fine structure of the cubic semiconductor compound Zn0.9Ni0.1S

The fine structure of a single crystal of the Zn_0.9Ni_0.1S cubic compound synthesized by the chemical transport method has been investigated at room temperature using thermal neutron diffraction. It has been found that the diffraction patterns of this compound, along with strong Bragg reflections of the facecentered cubic phase, include a system of diffuse maxima, which indicate the occurrence of a local deformation of the cubic structure by the Jahn-Teller nickel ions. Results of this experiment have been compared with the previously obtained data for the lightly doped Zn_{1 ? x} Ni _x Se single crystal (x = 0.002).     

Structural deformations of the cubic lattice of the Zn1 ? x Fe x Se (x = 0.001) crystal

The structural state of a Zn_{1 ? x} Fe _x Se (x = 0.001) crystal has been studied using thermal neutron diffraction. The diffraction patterns of the cubic crystal have been found to contain diffuse scattering regions concentrated in the vicinity of the strong Bragg reflections. It has been shown that the diffuse scattering effects are due to local transverse displacements of the crystal lattice atoms, and these displacements are induced by iron ions that demonstrate the static Jahn-Teller effect of the tetragonal type in the ZnSe compound.     

Magnetic phase transitions in Nd<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Ca<Emphasis Type="Italic">x</Emphasis>MnO<Subscript>3</Subscript> manganites

The magnetic properties of manganites of the Nd_1?xCa_xMnO₃ system with x≤0.15 have been studied. It is shown that, in the 0.06≤x≤0.1 interval, the results can be interpreted using a model according to which the concentrational transition from a weakly ferromagnetic (WFM) state (x=0) to a ferromagnetic (FM) state (x>0.15) proceeds via a mixture of the exchange-coupled FM and WFM phases. In the vicinity of T=9 K, samples with 0.06≤x≤0.1 exhibit a spontaneous magnetic phase transition involving reorientation of the magnetization vectors of the WFM and the exchange-coupled FM phases. In the temperature interval between 5 and 20 K, a sample with the composition Nd^0.92Ca^0.08MnO^2.98 exhibits metamagnetic behavior. Magnetic phase diagrams in the H?T and T?x coordinates are presented. The appearance of the spin-reorientation transitions is explained in terms of the magnetic analog of the Jahn-Teller effect with allowance for the fact that, according to the neutron diffraction data, the magnetic moments of neodymium ions in the FM phase are parallel to the magnetic moments of manganese ions.     

Study of the KNO<Subscript>3</Subscript>–Al<Subscript>2</Subscript>O<Subscript>3</Subscript> system by differential scanning calorimetry

The structural and the thermodynamic properties of potassium nitrate KNO₃ and its composites with nanosized aluminum oxide Al₂O₃ have been studied by differential scanning calorimetry. It has been found that an amorphous phase forms in composites (1–x)KNO_3–xAl₂O₃. The thermal effect corresponding to this phase has been observed at 316°C. It has been found that the phase transition heats of potassium nitrate decreased as the aluminum oxide fraction increased.     

Phase transitions and optical properties in 〈001〉 (1−<Emphasis Type="Italic">x</Emphasis>)PbZn<Subscript>1/3</Subscript>Nb<Subscript>2/3</Subscript>O<Subscript>3</Subscript>−<Emphasis Type="Italic">x</Emphasis>PbTiO<Subscript>3</Subscript> single crystals

The effect of a constant electric field (0 < E < 5 kV/cm) on the optical properties of PbZn_1/3Nb_2/3O₃?xPbTiO₃ (PZN-xPT) crystals with x = 7 and 9% has been analyzed. It has been shown that, at temperatures close to the temperature of the transition from the rhombohedral [R(X)] phase to the tetragonal (T) phase, two induced phase transitions are observed in the electric field, which are associated with the appearance of new intermediate phases M_a and M_c [R(X)-M_a-M_c-T]. Correlation between these two transitions and the PbTiO₃ content x has been found. The E-T phase diagrams have been obtained. The M_c phase in PZN-9PT crystals is found to remain the ground state after the removal of the electric field, whereas the M_c phase in PZN-7PT crystals is metastable and is transformed into the M_a phase after the removal of the electric field.     

Lattice,electrical, and magnetic effects in lanthanum manganites La1−x Sr x MnO3 (x = 0.125, 0.150, 0.175)

The temperature dependences of the velocities of transverse and longitudinal hypersound in lanthanum strontium manganites of the composition La_1−x Sr _x MnO₃ (x = 0.125, 0.150, 0.175) have been measured at frequencies of 0.5–0.7 GHz. The structural phase transitions have been revealed, and their positions have been confirmed by data on the electrical resistance and magnetic measurements performed using the same samples. The results obtained have been analyzed in the framework of the model of competing Jahn-Teller distortions and magnetic ordering. The anomalies observed in the behavior of the velocities of longitudinal hypersound have been attributed to the local Jahn-Teller distortions, and their suppression due to the magnetic ordering has been considered a possible factor responsible for the colossal magnetoresistance.     

A study of the phase diagrams of (NH4)3Ga1−x ScxF6 ammonium cryolites

This paper reports on the results of analyzing p-T and x-T phase diagrams and calorimetric properties of solid solutions in (NH₄)₃Ga_1?x Sc_xF₆ cryolites with scandium concentrations x=0.0, 0.1, 0.35, 0.4, 0.6, 0.8, and 1.0. The thermodynamic parameters of the phase transitions observed in the studied compounds are determined. The generalized phase diagram and successive structural transformations in a series of (NH₄)₃ Me ³⁺F₆ ammonium cryolites are discussed.     

Structural and magnetic transformations in the GdMn2Hx hydrides

Powder samples of GdMn₂H_x hydrides, with 0⩽x⩽4.3, have been characterized by X-ray analysis and SQUID magnetometry for temperatures ranging between 4 and 375 K. The observed phase transformations as a function of temperature and hydrogen concentration are discussed and explained. The correlated changes of magnetization and susceptibility have been analyzed and the temperature dependent development of magnetic ordering of Mn and Gd atoms as a function of temperature and hydrogen content has been discussed. The structural and magnetic phase diagrams have been proposed.     

Influence of the Jahn-Teller effect on the structural, magnetic, and electrical properties of lightly doped manganites

Features of the structural, magnetic and electric properties in lightly doped La_1?x Sr _x MnO₃ (0.12 < x < 0.18) manganites are studied. Agreement between the types of orbital ordering and the local cooperative Jahn-Teller distortion octahedra is established. The interaction between the Jahn-Teller effect and magnetic ordering is described.     

Investigation into phase diagrams of the fluorine-oxygen system: Ferroelastic-antiferroelectric (NH4)2WO2F4-(NH4)2MoO2F4

Thermal, physical, structural, optical, and dielectric investigations have been performed for oxyfluoride solid solutions (NH₄)₂W_{1 — x} Mo _x O₂F₄ (x = 0, 0.1, 0.2, 0.3, 0.4, 0.6, 0.8, 1). The character of the influence of the chemical and hydrostatic pressures on the stability of the parent (space group Cmcm) and distorted ferroelastic and antiferroelectric phases has been determined by analyzing the temperature-pressure, unit cell volume-composition, and temperature-composition phase diagrams. The specific features of the nature and mechanism of the phase transitions have been discussed using the available data on the structural, entropy, and dielectric parameters.     

Crystal-chemical effect of the thermodynamic history on the composition-temperature phase diagrams of (Na,Li)NbO3 and (Na,K)NbO3 solid solutions

Composition (x)-temperature (T) phase diagrams obtained for the first time for single-crystalline (Na,Li)NbO₃ (system I) and (Na,K)NbO₃ (system II) niobates are compared with the known phase diagrams for ferroelectric niobate ceramics prepared by various techniques (standard firing and hot pressing). In system I, the thermodynamic history (process conditions) is shown to have a pronounced effect on the diagrams throughout the range of perovskite stability, while in system II, the effect is the most significant at low potassium concentration (x≲0.15). These data are associated with a small value of the tolerance factor t of the solid solutions, whose properties are sensitive to the thermodynamic history. Small (≲0.9–0.93) values of t indicate the “porosity” of the structure of solid solutions I and II in the above concentration ranges. Under these condi-tions, polarization-and rotation-related structure instabilities compete on equal terms and substitutional and interstitial solid solutions may coexist.     

Cooperative Jahn-Teller effect in the mixed crystal system (Tbx,Tm1−x)AsO4

Single crystals of the system (Tb_x,Tm_1?x)AsO₄ have been investigated by means of optical absorption spectroscopy, birefringence and specific heat. Over the entire concentration range we observe a cooperative Jahn-Teller distortion. The phase transition may be approximated in mean field theory, taking into account that due to local strains part of the Tb and Tm ions are rendered Jahn-Teller inactive, an effect which is much more pronounced on the Tm (x ? 0) than on the Tb (x ? 1) side.     

Thermodynamic modelling of the cerium–oxygen system

The published data for the thermochemical properties and phase relationships of the cerium–oxygen system have been critically examined. No major inconsistencies in the experimental database have been found. Thermodynamic model parameters of all phases, i.e., liquid, fcc-Ce, bcc-Ce, A-, H-, and X-Ce₂O_3−x, Ce₃O_5±x (Mn₂O₃-type), CeO_2−x, as well as Ce₁₁O₂₀, Ce₆₂O₁₁₂, Ce₄₀O₇₂, Ce₁₉O₃₄, Ce₉O₁₆, and Ce₇O₁₂ have been derived by the least-squares minimization procedure using Thermo-Calc® software. The models are simple to be compatible with the standard Gibbs energy minimization procedure, but provide enough flexibility to account for the crystal structure, defect chemistry, and thermodynamic properties of phases in the Ce–O system. The backward compatibility of the refined parameters with experimental data has been demonstrated by calculation of phase and property diagrams. The Ce–O phase diagram in the whole range of compositions and at elevated temperature, a complete list of invariant reactions as well as the enthalpy and entropy of formation of Ce_nO_2n −2m phases are presented for the first time.     

Structural study of Pr1−xCaxMnO3 and Y1−xCaxMnO3 perovskites

The structural properties of Prx_1?xCa_xMnO₃ and Y_1?xCa_xMnO₃ perovskite systems were studied by X-ray and magnetic susceptibility measurements. The differences in the structural properties of both systems are attributed to the differences of tolerance factors, i.e. of ionic radii of the ions present and the results are interpreted as being due to simultaneous action of steric effect, orbit-lattice interactions of Mn³⁺ ions and Coulomb interactions among 3d electrons. Their individual contributions depending on the compositions are analyzed. Besides the usual cooperative Jahn-Teller effect existing in PrMnO₃ a new type of transformation was found which is connected, under condition of Mn³⁺ ? Mn⁴⁺ valency migration, with the formation of local Jahn-Teller distortions. It is characterized by the equality of v_hop and v_phon at a critical temperature T_crit; it has been found that T_crit depends only very weakly on the composition. A correpsonding O'→O change in the yttrium system is, however, rather continuous which is explained by a strong influence of the cooperative buckling effect. An analysis of the magnetic data points to the presence of double exchange in the praseodymium system at high temperatures, while at low temperatures this mechanism applies only in the region, where cooperative Jahn-Teller effect exists, i.e. at x0.4.     

Dielectric investigations of solid solutions SrTiO3-KTaO3 and SrTiO3-KNbO3

The temperature dependences of the dielectric constant and dielectric hysteresis loops in ceramic samples of (1 ? x)SrTiO_3?x KNbO₃ and (1 ? x)SrTiO_3?x KTaO₃ (0 ≤ x ≤ 0.3) solid solutions prepared using different heat treatments have been investigated. Phase diagrams of the studied solid solutions have been constructed in the T-x coordinates. It has been shown that, after quenching of samples (spontaneous cooling at room temperature after long-term heating at the sintering temperature of the ceramic samples), the temperature of the induced phase transition increases because of the weakening of random electric fields associated with nonisovalent impurities due to their “frozen” nonequilibrium redistribution. For small concentrations x, strong dielectric relaxation is observed in the temperature range of 150–250 K. A model of relaxing centers, which is based on the local charge compensation of heterovalent impurities, has been proposed.     

Magnetic phase diagrams of Mn(Nb0.5Ta0.5)2O6

The magnetic phase diagrams of Mn(Nb_0.5Ta_0.5)₂O₆ have been determined by means of neutron diffraction. Two spin-flop-transitions G_xA_z → A_xG_z → G_y have been detected in a magnetic field parallel to the x-direction. The first phase boundary increases as the temperature rises up to a triple point at 4.74 K and 20.5 kOe, whereas the second phase boundary decreases until another triple point at 4.55 K and 35.5 kOe is reached. In fields parallel to the z-direction a transition G_xA_z → G_xG_z has been revealed, the phase boundary meets the paramagnetic one in a triple point at 4.65 K and 55 kOe.