Disorder and phase transitions in oxyfluoride (NH4)3Ta(O2)2F4

Calorimetric, X-ray, dielectric and DTA under pressure measurements have been performed on oxyfluoride (NH₄)₃Ta(O₂)₂F₄. The succession of nonferroelectric phase transitions was found associated with the order-disorder processes. The comparative analysis tantalate with related niobate has revealed the important role of the central atom in the physical properties behavior, mechanism of structural distortions and barocaloric effect in oxyfluorides with the eight-coordinated anionic polyhedra.     

Orientation disorder in ammonium elpasolites: Crystal structures of (NH4)3AlF6, (NH4)3TiOF5 and (NH4)3FeF6

Crystal structures of the known (NH₄)₃AlF₆(I) and (NH₄)₃FeF₆(III) and new (NH₄)₃TiOF₅(II) elpasolites were refined by localizing anions (F⁻, O²⁻) in four acceptable positions of the cubic system Fm3m (Z=4) with a=8.9401(3), 9.1104(3), 9.110(1) Å, respectively. According to the refinement data and a rather large entropy change due to fluorine (oxygen) octahedra disordering in the above compounds and in (NH₄)₃WO₃F₃(IV) elpasolite, it was found that fluorine (oxygen) atoms are randomly distributed in two ways, in general 192l position or in mixed 24e + 96j one. Statistics in fluorine (oxygen) distribution is, probably, the result of domain structure of the crystals.     

Isomorphy of structural phase transitions in LiTaOSiO4, LiTaOGeO4 and titanite, CaTiOSiO4

Structural phase transitions in LiTaOGeO₄ (LTGO) and LiTaOSiO₄ (LTSO) have been observed using differential scanning calorimetry, X-ray diffraction and MAS NMR spectroscopy. LTGO transforms from P2₁/c to C2/c space group symmetry at , while the isomorphic transition occurs at in LTSO. An analogous phase transition is known to occur in the structurally related mineral titanite, CaTiOSiO₄. Spontaneous strain accompanying this phase transition in LTSO is significantly stronger than in titanite. As in titanite non-vanishing strain components are observable for T_c<T<T_i, with a similar ratio T_i/T_c. MAS NMR spectroscopy in combination with computation of the electric field gradient by first principle methods confirms that the tetrahedral Li coordination environment is retained during the phase transitions in LTGO and in LTSO. In LTSO substantial motional narrowing is observed, indicating increased mobility of the Li cation above . The narrowing of the spinning sidebands is significantly modified immediately above and below the critical temperature.     

Structural phase transitions in Zn(CN)2 under high pressures

High pressure behavior of zinc cyanide (Zn(CN)₂) has been investigated with the help of synchrotron-based X-ray diffraction measurements. Our studies reveal that under pressure this compound undergoes phase transformations and the structures of the new phases depend on whether the pressure is hydrostatic or not. Under hydrostatic conditions, Zn(CN)₂ transforms from cubic to orthorhombic to cubic-II to amorphous phases. In contrast, the non-hydrostatic pressure conditions drive the ambient cubic phase to a partially disordered crystalline phase, which eventually evolves to a substantially disordered phase. The final disordered phase in the latter case is distinct from the amorphous phase observed under the hydrostatic pressures.     

Structural phase transitions in BaV6O11

BaV₆O₁₁ was synthesized under high pressures and crystallizes in a structure closely related to magnetoplumbite. [V(1)O₆]-octahedra share common edges and form a Kagomé lattice normal to the hexagonal [0 0 1] direction. The layers are connected in the direction of c via trigonal [V(3)O₅]-bipyramids and [V(2)O₆]-octahedra, which share common faces. The Ba-atoms are incorporated into cavities of the vanadium oxide framework and are coordinated by 12 oxygen atoms in the shape of a dodecahedron.Three magnetic anomalies at approximately 250, 115 and 75 K were detected in this compound. All of them are accompanied by anomalies in the specific heat measurement. To characterize possible structural transitions and determine the response of the structure to the magnetic anomalies, single crystal X-ray diffraction studies were carried out in the temperature range from 293 to 80 K. At 250 K the compound undergoes a structural phase transition. The space group above the transition temperature is P6₃/mmc, at lower temperature the symmetry reduces to P6₃mc. For the refinements in P6₃mc an inversion twin model was used, this way accounting for the loss of the center of symmetry. The structural phase transition is characterized by a small displacement of the V(1)-atom (forming the Kagomé lattice) out of its central position in the octahedra. As a consequence part of the octahedral edges/angles are increased, while the opposite ones are decreased. One limiting surface of the octahedral sheet is corrugated, while the other one is smoothened with respect to the high-temperature structure. This deformation of the octahedral sheets leads to the corresponding geometrical changes in the other coordination polyhedra.The structural response to the magnetic anomaly at 115 K is weak and mainly observable in the geometric parameters concerning the [V(1)O₆]-octahedra and [V(3)O₅]-bipyramids. This may serve as a first indication that the corresponding central atoms play an important role in the mechanism of the magnetic phase transition.     

Phase transitions in the A2BX4-compound: Tetramethylammonium tetrachlorozincate tetrachlorocuprate, [(CH3)4N]2Zn0.5Cu0.5Cl4, and room temperature crystal structure determination

Preparation, crystal structure, and infra-red absorption spectra are reported for the first material in an A₂BX₄ compound with metal transition substitution in tetrahedral anion, tetramethylammonium tetrachlorozincate tetrachlorocuprate: [(CH₃)₄N]₂Zn_0.5Cu_0.5Cl₄. The calorimetric study shows five endothermic peaks at 248.75, 271.75, 278.6, 286.7, and 293.7 K. The determination of unit cell in the 240–298 K temperature range confirms those observed by the DSC technique. At room temperature, the compound crystallizes in an orthorhombic system (P2₁ cn space group) with Z = 4 and the following unit cell dimensions: a = 8.988 (3), b = 15.527 (2) and c = 12.269 (4) ?. The structure was solved by using 1986 independent reflections down to an R value of 0.048. The crystal structure consists of alternating organic-inorganic [(TMA)⁺/(Cu)ZnCl₄²⁻] layers and organic sheets (TMA)²⁺. All Organic groups and (Cu)ZnCl₄²⁻ are not disordered. Their main geometrical features are those commonly observed in the atomic arrangements of (TMA)₂ZnCl₄ and (TMA)₂CuCl₄. The text was submitted by the authors in English.     

NQR and phase transitions in mixed A2BX6 compounds

³⁵Cl NQR frequency and phase transition temperature were investigated in the mixed crystals (A_xK_1?x) SnCl₆ (A = Rb, NH₄) and K₂ (Re_x Sn_1?x) Cl₆. The frequency and the intensity of the NQR signal were measured in the temperature range 100 K to 300 K for different chemical compositions. Phase transition temperatures were determined from the modifications in the line pattern. The observed change of the transition temperature as a function of concentration x can be fitted by the relation T_c(x) = T_c(O) (1 + a x)/(1 + b x). This formula is explained in the context of the virtual crystal approximation and the Landau theory.     

Crystal structures and phase transitions of Sr2CrSbO6

Sr₂CrSbO₆ was synthesized by the conventional solid-state reaction process. X-ray powder diffraction (XRPD) and neutron powder diffraction (NPD) has been used to reinvestigate the structure at room temperature and to study the phase transitions at high- and low-temperature. Rietveld analysis revealed that Sr₂CrSbO₆ crystallizes at room temperature in a monoclinic system having a space group I2/m, with a=5.5574(1) Å; b=5.5782(1) Å; c=7.8506(2) Å and β=90.06(2), no P2₁/n space group as was previously reported. The high-temperature study (300-870 K) has shown that the compound presents the following temperature induced phase-transition sequence: I2/m-I4/m-Fm-3m. The low-temperature study (100-300 K) demonstrated that the room-temperature I2/m monoclinic symmetry seems to be stable down to 100 K.     

Pressure induced structural phase transition of OsB2: First-principles calculations

Orthorhombic OsB₂ was synthesized at 1000 °C and its compressibility was measured by using the high-pressure X-ray diffraction in a Diacell diamond anvil cell from ambient pressure to 32 GPa [R.W. Cumberland, et al. (2005)]. First-principles calculations were performed to study the possibility of the phase transition of OsB₂. An analysis of the calculated enthalpy shows that orthorhombic OsB₂ can transfer to the hexagonal phase at 10.8 GPa. The calculated results with the quasi-harmonic approximation indicate that this phase transition pressure is little affected by the thermal effect. The calculated phonon band structure shows that the hexagonal P 6₃/mmc structure (high-pressure phase) is stable for OsB₂. We expect the phase transition can be further confirmed by the experimental work.     

The low-temperature form of Rb2KCrF6 and Rb2KGaF6: The first example of an elpasolite-derived structure with pentagonal bipyramid in the B-sublattice

The crystal structure of the low-temperature forms of Rb₂KCrF₆ and Rb₂KGaF₆ has been solved on single crystal. The symmetry is tetragonal with F4/m space group; the unit cell parameters are: , for Rb₂KCrF₆ at and , for Rb₂KGaF₆ at . The relationships between the parameters of the prototype cubic elpasolite, which is stable at high temperature, and the tetragonal superlattice of the low temperature form have been established. Considering the general formulation A₂BB′F₆, the cationic positions in the A and (B,B′) sublattices remain identical in the two allotropic varieties. The main originality of the structure concerns the environment of 4/5 of the potassium atoms (B sublattice) which is transformed from octahedra into pentagonal bipyramids sharing edges with adjacent B′F₆ octahedra containing Cr or Ga. The displacive phase transition is simply explained by the rotation of 45° in the (a,b) plane of 1/5 of the B′F₆ (B′=Cr, Ga) octahedra. The similarity of this phase transition and the transformation of perovskite into tetragonal tungsten bronze (TTB) will be discussed.     

Order-disorder transition in the complex lithium spinel Li2CoTi3O8

Li₂CoTi₃O₈ has an ordered Li₂BB′₃O₈ spinel structure, space group P4₃32, at room temperature with 3:1 ordering of Ti and Li on the octahedral sites, and Li, Co disordered over the tetrahedral site. Rietveld refinement of variable temperature neutron powder diffraction data has shown an order-disorder phase transition in Li₂CoTi₃O₈ which commences at ∼500 °C with Li and Co mixing on the tetrahedral and 4-fold octahedral sites and is complete at a first order structural discontinuity at ∼915 °C. The fraction of Ti on the 12-fold octahedral site exhibits a small decrease with increasing temperature, which may suggest that the disordering involves all three cations. Above 930 °C, the structure, space group Fd3¯m, has Li, Co and Ti sharing a single-octahedral site and Li, Co sharing a tetrahedral site, although Co still exhibits a preference for tetrahedral coordination. A labelling scheme for ordered and partially ordered 3:1 spinels is devised which focuses on the occupancy of the Li,B cations.     

Structural phase transitions in the relaxor ferroelectric Pb2Bi4Ti5O18

The relaxor ferroelectric Pb₂Bi₄Ti₅O₁₈ has been studied by Rietveld refinement of powder neutron diffraction data collected at temperatures of 100, 250 and 400 °C. Our refinements are compatible with the ‘average’ crystal structure of Pb₂Bi₄Ti₅O₁₈ undergoing the phase transition sequence F2mm→I4mm→I4/mmm as a function of increasing temperature, with the latter phase being observed above the known ferroelectric Curie temperature, T_m, and the intermediate phase consistent with a previously observed dielectric anomaly around 207 °C. The results are, however, in conflict with both observation of a symmetry lowering (to space group B2eb) in the lowest temperature phase, observed by electron diffraction, and also with electrical property measurements, which suggest both a- and c-axis polarisation up to T_m. Nevertheless, these crystallographic results are consistent with the observation of relaxor behaviour in this material, and underline the importance of considering ‘long-range’ versus ‘local’ structural effects in relaxor materials.     

The Jahn-Teller distortion and cation ordering in the perovskite Sr2MnSbO6

The perovskite Sr₂MnSbO₆ has been synthesized using conventional ceramic techniques and structurally characterized using high-resolution powder X-ray and neutron diffraction. The structure is tetragonal in space group I4/m. The octahedra were found to feature Jahn-Teller (JT) distortion due to the presence of Mn³⁺, and this is identified as strongly contributing to the octahedral tilting. Evidence for B-site cation ordering is presented however there is extensive anti-site disorder. The disordering of the Mn³⁺ and Sb⁵⁺ cations is believed to be a result of the similar size of these two cations and the polarizability of the Sb⁵⁺ cation. The structure was found to undergo a transition to cubic symmetry at 521 °C with removal of the octahedral tilting leading to the quenching of the JT distortion. This phase transition was found to be continuous and tricritical in nature.     

Synthesis, crystal structure, phase transition and thermal behaviour of a new dabcodiium hexaaquanickel(II) bis(sulphate), (C6H14N2)[Ni(H2O)6](SO4)2

A new dabcodiium-templated nickel sulphate, (C₆H₁₄N₂)[Ni(H₂O)₆](SO₄)₂, has been synthesised and characterised by single-crystal X-ray diffraction at 20 and −173 °C, differential scanning calorimetry (DSC), thermogravimetry (TG) and temperature-dependent X-ray powder diffraction (TDXD). The high temperature phase crystallises in the monoclinic space group P2₁/n with the unit-cell parameters: a = 7.0000(1), b = 12.3342(2), c = 9.9940(2) Å; β = 90.661(1)°, V = 862.82(3) Å³ and Z = 2. The low temperature phase crystallises in the monoclinic space group P2₁/a with the unit-cell parameters: a = 12.0216(1), b = 12.3559(1), c = 12.2193(1) Å; β = 109.989(1)°, V = 1705.69(2) Å³ and Z = 4. The crystal structure of the HT-phase consists of Ni²⁺ cations octahedrally coordinated by six water molecules, sulphate tetrahedra and disordered dabcodiium cations linked together by hydrogen bonds. It undergoes a reversible phase transition (PT) of the second order at −53.7/−54.6 °C on heating-cooling runs. Below the PT temperature, the structure is fully ordered. The thermal decomposition of the precursor proceeds through three stages giving rise to the nickel oxide.     

Structural studies of the disorder and phase transitions in the double perovskite Sr2YTaO6

The evolution of the crystal structure of the double perovskite Sr₂YTaO₆ from room temperature to 1250 °C has been studied using powder neutron and synchrotron X-ray diffraction. At room temperature Sr₂YTaO₆ crystallises in a monoclinic superstructure with the space group P2₁/n. The tilting of the octahedra evident in the room temperature structure is progressively lost on heating, resulting in a sequence of phase transitions that ultimately yields the cubic structure in space group Fm3?m. The high temperature tetragonal and cubic phases are characterised by strongly anisotropic displacements of the anions. The amount of defects in the crystal structure of Sr₂YTaO₆ is found to be sensitive to the preparative method.     

Effect of metal doping on the low-temperature structural behavior of thermoelectric β-Zn4Sb3

The low-temperature structural phase transitions of Bi, Pb, In and Sn-doped samples of thermoelectric Zn₄Sb₃ have been characterized on crystals grown from molten metal fluxes, using electrical resistance and single crystal X-ray diffraction measurements. Room temperature stable, disordered, β-Zn₄Sb₃ undergoes two phase transitions at 254 and 235 K to the consecutively higher ordered phases α and α′, respectively. The ideal crystallographic composition of α-Zn₄Sb₃ is Zn₁₃Sb₁₀. The α-α′ transformation is triggered by a slight and homogenous Zn deficiency with respect to this composition and introduces a compositional modulation in the α-Zn₄Sb₃ structure. When preparing β-Zn₄Sb₃ in the presence of metals with low melting points (Bi, Sn, In, Pb) the additional metal atoms are unavoidably incorporated in small concentrations (0.04-1.3 at%) and act as dopants. This incorporation alters the subtle balance between Zn disorder and Zn deficiency in Zn₄Sb₃ and has dramatic consequences for its low-temperature structural behavior. From molten metal flux synthesis it is possible to obtain (doped) Zn₄Sb₃ samples which (1) only display a β-α transition, (2) only display a β-α′ transition, or (3) do not display any low-temperature phase transition at all. Case (2) provided diffraction data with a sufficient quality to obtain a structural model for highly complex, compositionally modulated, α′-Zn₄Sb₃. The crystallographic composition of this phase is Zn₈₄Sb₆₅.     

Infrared spectroscopic study of the local structural changes across the metal insulator transition in nickel-doped GdBaCo2O5.5

Phonons in GdBaCo₂O_5.5 have been identified using infrared spectroscopy and their mode assignments have been carried out using ab initio lattice dynamical calculations. Metal insulator transitions in undoped and nickel-doped GdBaCo₂O_5.5 have been probed using infrared absorption spectroscopy. The phonon modes corresponding to the bending mode of the CoO₆ octahedra/pyramids are seen to soften, broaden and develop an asymmetry across the insulator-metal transition pointing to extensive electron phonon interaction effects in these systems. Correlated changes of the phonon line shape parameters associated with the transition indicate a suppression of T_MIT with increased nickel doping of the cobalt sublattice. Temperature dependence of the octahedral stretching mode frequencies in undoped GdBaCo₂O_5.5 points to distinct structural distortions accompanying the high temperature metallic transition.     

Impact of metal substitutions for cobalt in YBaCo4O7

The “114” YBaCo₄O₇ cobaltite undergoes structural transition just beyond room temperature at T_S∼310 K. Correspondingly, its signature in the physical properties is detected by T-dependent measurements of electrical resistivity, magnetic susceptibility and thermoelectric power. It is found that low-level substitutions of divalent (M=Zn²⁺) or trivalent (M=Ga³⁺, Al³⁺) cations for cobalt according to the YBaCo_4−xM_xO₇ formula with x?0.4 have a strong impact upon this transition. On the one hand, Zn²⁺ substitutions preserve the transition but with T_S decreasing as x increases. On the other hand, for x=0.2 Ga³⁺ or Al³⁺, the transition is suppressed, i.e., for only 5% trivalent foreign cation substituted for cobalt. Though at first, this contrasted behaviour between divalent and trivalent substituting cations appears to be linked to the opposite evolution of hole carriers “Co³⁺” concentration with x, a possible destabilization of 3Co²⁺: 1Co³⁺ charge ordering induced by the M³⁺ cations is considered.     

Diffusion paths formation for Cu ions in superionic Cu6PS5I single crystals studied in terms of structural phase transition

In order to understand the structural transformations leading to high ionic conductivity of Cu⁺ ions in Cu₆PS₅I argyrodite compound, the detailed structure analysis based on single-crystal X-ray diffraction has been performed. Below the phase transition at Cu₆PS₅I belongs to monoclinic, ferroelastic phase (space group Cc) with ordered copper sublattice. Above T_c delocalization of copper ions begins and crystal changes the symmetry to cubic superstructure with space group F-43c (, z=32). Finally, above increasing disordering of the Cu⁺ ions heightens the symmetry to F-43m (, z=4). In this work, the final structural model of two cubic phases is presented including the detailed temperature evolution of positions and site occupation factors of copper ions (R₁=0.0397 for F-43c phase, and 0.0245 for F-43m phase). Possible diffusion paths for the copper ions are represented by means of the atomic displacement factors and split model. The structural results coincide well with the previously reported non-Arrhenius behavior of conductivity and indicate significant change in conduction mechanism.     

Structural characterisation of the perovskite series SrxCa1−x−yNdyMnO3: Influence of the Jahn-Teller effect

The crystal structures of the perovskite manganites Sr_xCa_1−x−yNd_yMnO₃ with y=0.1 or 0.2 have been investigated using synchrotron X-ray powder diffraction. At room temperature the structures change from depending on the cation distribution, the different structures exhibiting different tilts of the MnO₆ octahedra. High temperature diffraction measurements demonstrate the presence of, an apparently continuous, isosymmetric I4/mcm to I4/mcm phase transition associated with the removal of long range orbital ordering. Heating the manganites to still higher temperatures results in a continuous transition to the cubic structure. A feature of such transitions is the continuous evolution of the octahedral tilt angle through the I4/mcm to I4/mcm phase transition. The orthorhombic structures do not exhibit orbital ordering and although a first order transition to the tetragonal structure is observed in Sr_0.4Ca_0.5Nd_0.1MnO₃, this high temperature tetragonal structure does not exhibit orbital ordering.