Structural changes concurrent with ferromagnetic transition

Ferromagnetic transition has generally been considered to involve only an ordering of magnetic moment with no change in the host crystal structure or symmetry, as evidenced by a wealth of crystal structure data from conventional X-ray diffractometry (XRD). However, the existence of magnetostriction in all known ferromagnetic systems indicates that the magnetic moment is coupled to the crystal lattice; hence there is a possibility that magnetic ordering may cause a change in crystal structure. With the development of high-resolution synchrotron XRD, more and more magnetic transitions have been found to be accompanied by simultaneous structural changes. In this article, we review our recent progress in understand- ing the structural change at a ferromagnetic transition, including synchrotron XRD evidence of structural changes at the ferromagnetic transition, a phenomenological theory of crystal structure changes accompanying ferromagnetic transitions, new insight into magnetic morphotropic phase boundaries (MPB) and so on. Two intriguing implications of non-centric symmetry in the ferromagnetic phase and the first-order nature of ferromagnetic transition are also discussed here. In short, this review is intended to give a self-consistent and logical account of structural change occurring simultaneously with a ferromagnetic transition, which may provide new insight for developing highly magneto-responsive materials.     

Magnetic susceptibility and Eu Mössbauer studies on cubic ternary compounds: EuPtSi and EuPdSi

Two new equiatomic ternary compounds, EuPtSi and EuPdSi, have been synthesized and are found to crystallize in the cubic LaIrSi type structure. The magnetic susceptibility of both compounds follows Curie-Weiss behavior in the temperature range 10 to 300 K with an effective magnetic moment close to that of Eu²⁺ moment. The paramagnetic Curie temperatures are 5 K for EuPtSi and 9 K for EuPdSi. There is no clear indication of magnetic ordering in the susceptibility of both the compounds down to 4.2 K. However, ¹⁵¹Eu Mössbauer studies show a hyperfine split pattern in EuPtSi at 4.2 K indicating the onset of magnetic ordering. The ¹⁵¹Eu isomer shifts are temperature independent and are characteristic of the divalent Eu ion. All these results establish that the Eu ions are in a stable divalent state in these compounds.     

Evidence for insulating behavior in the electric conduction of (NH(3))K(3)C(60) systems

Microwave study using the cavity perturbation technique revealed that the conductivity of the antiferromagnet (NH(3))K(3-x)Rb(x)C(60) at 200 K is already 3-4 orders of magnitude smaller than those of superconductors, K(3)C(60) and (NH(3))(x)NaRb(2)C(60), and that the antiferromagnetic compounds are insulators below 250 K without metal-insulator transitions. The striking difference in the magnitude of the conductivity between these materials strongly suggests that the Mott-Hubbard transition in the ammoniated alkali fullerides is driven by a reduction of lattice symmetry from face-centered-cubic to face-centered-orthorhombic, rather than by the magnetic ordering.     

Magnetic and quadrupolar properties of PrPb3

The cubic rare earth intermetallic compound PrPb₃ (AuCu₃-type structure) undergoes a transition at 0.35 K: as it is a Van Vleck paramagnet, the low temperature phase was assumed to be quadrupolarly ordered. In order to specify this possibility, we first discuss the cubic level scheme using specific heat and first-order magnetic susceptibility results; afterwards we present an extensive study of the two (tetragonal and trigonal) symmetry lowering modes, investigated in the cubic paramagnetic phase by means of parastriction and third-order magnetic susceptibility. For the tetragonal symmetry, the quadrupolar pair interactions appear as negative, dominating the magnetoelastic coupling; as a result, the low temperature ordering may be antiferroquadrupolar, a new situation among rare earth intermetallics, the TmZn and TmCd ordering being ferroquadrupolar.     

Low-temperature structural phase transitions of TbB4 and ErB4 studied by high resolution X-ray diffraction and profile analysis

The isostructural rare earth tetraborides TbB₄ and ErB₄ of tetragonal space group P4/mbm undergo structural phase transitions to orthorhombic symmetry around T = 80 K and T = 15 K, respectively. The lattice distortions have been investigated by individual peak profile analysis performed on high-precision X-ray data. The experimental and analytical processing is outlined. The deviations from a tetragonal cell at 4.2 K are 2 × 10⁻² Å for TbB₄ and 3 × 10⁻³ Å for ErB₄. The relative volume change between 300 and 4.2 K is less than 10⁻³ in the TbB₄ lattice and 2.3 × 10⁻³ in ErB₄.The tetragonal to orthorhombic distortions are discussed in the context of the antiferromagnetic phase transitions of TbB₄ at T_N = 43 K and of ErB₄ at T_N = 13 K. The relationship between the structural and magnetic phase transitions differs for the two compounds. In TbB₄, the structural transition, which occurs at a definitely higher temperature than the magnetic ordering, is assumed to be driven by a strong electron-lattice coupling or by an electronic quadrupole-quadrupole interaction. In ErB₄, the structural distortion is attributed to magnetostrictive effects occurring simultaneously with the magnetic ordering process.     

CaCuxMn3-xMn4O12的结构及输运性质研究

湿化学反应法制备了CaCuxMn3-xMn4 O12(x=0.2,0.4,0.6,0.8,1.0,1.2,1.4)系列材料的前驱体,然后通过高温烧结做成样品,进一步丰富了这类样品的研究内容.X射线衍射表明掺杂Cu2+在x=0.2到x=1.4范围内这些材料都能够成单相.通过Rietveld全谱拟合的方法分析,结果表明随掺...     

Structural and magnetic studies on RPtIn deuterides (R=Tb,Er, Tm)

In this communication, structural and magnetic properties of RPtInD_1.3 (R=Tb, Er, Tm) deuterides are reported. For the first time deuterium-rich compounds were synthesized for the RPtIn family. The investigated deuterides crystallize with the hexagonal ZrNiAl-type crystal structure, with slightly different lattice constants with respect to the basic compounds. In general, the a-lattice constant exhibit contraction, while the c-lattice constant tends to increase upon introducing deuterium. The compounds with Tb and Er shows magnetic ordering at 95 K and 15.5 K, respectively. On the other hand, for Tm based sample no magnetic ordering was evidenced down to 2 K.     

Successive structural phase transitions in Pr<Subscript>0.5</Subscript>Sr<Subscript>0.5</Subscript>CoO<Subscript>3</Subscript> in the range 10–1120 K

The crystal and magnetic structures of the Pr_0.5Sr_0.5CoO₃ metallic ferromagnet have been studied using neutron diffraction and synchrotron radiation. Successive structural transitions with the reduction of the crystal symmetry from cubic (space group Pm3m) to rhombohedral (\(R\bar 3c\), ～800 K), orthorhombic (Imma, ～300 K) and, then, to triclinic at ～120 K are detected during cooling from 1120 K. The transition from the orthorhombic system to a phase with a lower symmetry is characterized by a sharp change in the anisotropy of the unit cell, which indicates the partial ordering of the e _g orbitals of cobalt. The accompanying change in the interatomic distances and valence angles give rise to an anomaly in the temperature dependence of the magnetic susceptibility at T ≈ 120 K. The ordered magnetic moment μ_Co ≈ 2μ_B corresponds to the assumption of the intermediate spin state of Co³⁺ ions and the mixture of low- and intermediate-spin states of Co⁴⁺ ions.     

Single crystal and powder EPR study of trivalent gadolinium in Cs2NaBiCl6 in the 30-300 K interval

A crystalline electric field cubic symmetry site has been reported for Gd³⁺ in Cs₂NaBiCl₆ at room temperature. This host exhibits an apparent structural transformation below 100 K that is completely reversible. However, an EPR examination for a powdered sample of Cs₂NaBiCl₆:Gd³⁺ clearly demonstrates that there are no new large crystalline electric field symmetry sites arising between the transition temperature (100 K) and 30 K, suggesting, therefore, that the site symmetry remains predominantly cubic even at temperatures close to 30 K. In order to substantiate this statement, a computer EPR powder simulation was performed using the single-crystal-spin-Hamiltonian parameters obtained from the three different sites that emerge from the original site while observed at 30 K. A remarkable agreement is observed while comparing the computer-simulated data with that of powdered experimental data. It is important to mention here that several attempts were done trying to fit the observed new spectra to lower crystalline field symmetries, however, our best analytical adjustment was obtained with the cubic spin-Hamiltonian.Below 30 K, new structural transitions are present and the lattice loses its original cubic nature. However, at 10 K the EPR spectrum of the crystal again shows only seven lines that are very broad. This new spectrum cannot be fitted with previously used cubic spin-Hamiltonian parameters.     

Critical and multicritical behavior in the Ising–Heisenberg universality class

Critical behavior of three-dimensional classical frustrated antiferromagnets with a collinear spin ordering and with an additional twofold degeneracy of the ground state is studied. We consider two lattice models, whose continuous limit describes a single phase transition with a symmetry class differing from the class of non-frustrated magnets as well as from the classes of magnets with non-collinear spin ordering. A symmetry breaking is described by a pair of independent order parameters, which are similar to order parameters of the Ising and O(N) models correspondingly. Using the renormalization group method, it is shown that a transition is of first order for non-Ising spins. For Ising spins, a second order phase transition from the universality class of the O(2) model may be observed. The lattice models are considered by Monte Carlo simulations based on the Wang–Landau algorithm. The models are a ferromagnet on a body-centered cubic lattice with the additional antiferromagnetic exchange interaction between next-nearest-neighbor spins and an antiferromagnet on a simple cubic lattice with the additional interaction in layers. We consider the cases N = 1, 2, 3 and in all of them find a first-order transition. For the N = 1 case we exclude possibilities of the second order or pseudo-first order of a transition. An almost second order transition for large N is also discussed.     

Orbital ordering and magnetic field effect in MnV2O4

We studied the structural properties of an orbital-spin-coupled spinel oxide, MnV2O4, mainly by single-crystal x-ray diffraction measurement. It was found that a structural phase transition from cubic to tetragonal and ferrimagnetic ordering occur at the same temperature (Ts,TN=57 K). The structural phase transition was induced also by magnetic field above Ts. In addition, magnetic-field-induced alignment of tetragonal domains results in large magnetostriction below Ts. We also found that the structural phase transition is caused by the antiferro-type ordering of the V t2g orbitals.     

Magnetoresistances and magnetic entropy changes associated with negative lattice expansions in NaZn13-type compounds LaFeCoSi

Magnetoresistances and magnetic entropy changes in NaZn13-type compounds La（Fel-xCox）11.9Si1.1 （x=0.04, 0.06, and 0.08） with Curie temperatures of 243 K, 274 K, and 301 K, respectively, are studied. The ferromagnetic ordering is accompanied by a negative lattice expansion. Large magnetic entropy changes in a wide temperature range from ～230 K to ～320 K are achieved. Raising Co content increases the Curie temperature but weakens the magnetovolume effect, thereby causing a decrease in magnetic entropy change. These materials exhibit a metallic character below Tc, whereas the electrical resistance decreases abruptly and then recovers the metal-like behaviour above Tc. Application of a magnetic field retains the transitions via increasing the ferromagnetic ordering temperature. An isothermal increase in magnetic field leads to an increase in electrical resistance at temperatures near but above Tc, which is a consequence of the field-induced metamagnetic transition from a paramagnetic state to a ferromagnetic state.     

Incommensurate magnetic structures in rhombohedral Heisenberg antiferromagnet

The phase diagram of the ground state has been calculated for a rhombohedral antiferromagnet of the R3m symmetry with frustrated exchange in the base plane and competition of exchanges between the nearest and next-nearest planes. The diagram contains phases of collinear antiferromagnetic ordering of various types separated by five incommensurate magnetic states of the helicoidal type, differing in the ordering type and in the direction of the modulation vector. The commensurate and incommensurate phases converge at multi-critical points lying on a line corresponding to an antiferromagnet with an undistorted simple cubic lattice.     

Microstrain sensitivity of orbital and electronic phase separation in SrCrO3

An orbital ordering transition and electronic phase coexistence have been discovered in SrCrO3. This cubic, orbitally-degenerate perovskite transforms to a tetragonal phase with partial orbital order. The tetragonal phase is antiferromagnetic below 35-40 K, whereas the cubic phase remains paramagnetic at low temperatures. The orbital ordering temperature (35-70 K) and coexistence of the two electronic phases are very sensitive to lattice strain. X-ray measurements show a preferential conversion of the most strained regions in the cubic phase. This reveals that small fluctuations in microstrain are sufficient to drive long range separation of competing electronic phases even in undoped cubic oxides.     

Magnetic properties and magnetocaloric effect of the Cr-based spinel sulfides Co_(1-x)Cu_xCr_2S_4

Crystallographic structure, magnetic properties, and magnetic entropy change of the Cr-based spinel sulfides Co_(1-x)Cu_xCr_2S_4(x = 0–0.8) have been investigated. All these compounds crystallize into the cubic spinel structure, the Cu substitution shrinks linearly the lattice constant at a ratio of 0.0223 per Cu atom in the unit cell, and enhances linearly the Curie temperature and the spontaneous magnetization at the rates of 18K and 0.33 μB/f.u. per Cu atom in the unit cell,respectively. All these compounds show a typical behavior of second order magnetic transition, and a room temperature magnetic entropy change of 2.57 J/kg·K is achieved for Co_(0.4)Cu_(0.6)Cr_2S_4.     

Effect of uniaxial strain on the structural and magnetic phase transitions in BaFe2As2

We report neutron scattering experiments probing the influence of uniaxial strain on both the magnetic and structural order parameters in the parent iron pnictide compound, BaFe2As2. Our data show that modest strain fields along the in-plane orthorhombic b axis can affect significant changes in phase behavior simultaneous to the removal of structural twinning effects. As a result, we demonstrate in BaFe2As2 samples detwinned via uniaxial strain that the in-plane C4 symmetry is broken by both the structural lattice distortion and long-range spin ordering at temperatures far above the nominal (strain-free) phase transition temperatures. Surprising changes in the magnetic order parameter of this system under relatively small strain fields also suggest the inherent presence of magnetic domains fluctuating above the strain-free ordering temperature in this material.     

Spontaneous symmetry-breaking vortex lattice transitions in pure niobium

We report an extensive investigation of magnetic vortex lattice (VL) structures in single crystals of pure niobium with the magnetic field applied parallel to a fourfold symmetry axis, so as to induce frustration between the cubic crystal symmetry and hexagonal VL coordination expected in an isotropic situation. We observe new VL structures and phase transitions; all the VL phases observed (including those with an exactly square unit cell) spontaneously break some crystal symmetry. One phase even has the lowest possible symmetry of a two-dimensional Bravais lattice. This is quite unlike the situation in high-Tc or borocarbide superconductors, where VL structures orient along particular directions of high crystal symmetry. The causes of this behavior are discussed.     

7Li NMR investigation of Li-Li pair ordering in the paraelectric phase of weakly substitutionally disordered K(1-x)Li(x)TaO3

Breaking of the average cubic symmetry in Li-doped potassium tantalate was observed with quadrupole-perturbed 7Li NMR at temperatures (150-400?K) far above the nominal glass transition temperature (≈50 K for Li concentration x=0.03). The observed spectrum consists of contributions from both isolated Li ions (i.e., with no nearest-neighbor Li) and from Li-Li pairs. The isolated Li ions move among six equivalent off-center sites in a potential having cubic symmetry. These have zero average electric field gradient and, hence, exhibit no quadrupole splitting. In addition, very low intensity, but well resolved, quadrupole satellites having a temperature-dependent splitting were observed. This splitting indicates that the various Li-Li pair configurations are not all equally probable. These are the first direct observations of biased Li ion ordering that persists in the paraelectric phase at temperatures high above the glass phase.     

Critical Properties of Mixed Ising Spin System with Different Trimodal Transverse Fields in the Presence of Single-Ion Anisotropy

Within the framework of an effective field approximation, the effects of single-ion anisotropy and different trimodal transverse fields of two sublattices on the critical properties of the mixed spin-1/2 and spin-1 Ising system are investigated on the simple cubic lattice. A smaller single-ion anisotropy can magnify magnetic ordering phases and a larger one can depress magnetic ordering phase for T-Ω_1/2 space at low temperatures, while a smaller single-ion anisotropy can hardly change the value of critical transverse field for T-Ω₁ space. On the other hand, influences of two different trimodal transverse fields concentrations on tricritical points and magnetic ordering phases take on some interesting results in T-D space. The main reason comes from the common action of single-ion anisotropy, different transverse fields and two trimodal distributions.     

Synthesis and structural determination of the new oxide fluoride BaFeO2F

Low temperature fluorination of BaFeO_3−x using poly(vinylidene fluoride) leads to the formation of the oxide fluoride BaFeO₂F. Mössbauer spectroscopy shows that this phase exhibits magnetic ordering at room temperature due to interactions between the Fe³⁺ ions, with an ordering temperature of 645 (±5) K. Neutron diffraction studies show that the phase has cubic symmetry and confirm the presence of magnetic ordering (G-type antiferromagnetic) at room temperature.