A new commensurate phase on the theoretical phase diagram of the [N(CH<Subscript>3</Subscript>)<Subscript>4</Subscript>]<Subscript>2</Subscript>CuCl<Subscript>4</Subscript> crystal

A theoretical phase diagram of the [N(CH₃)₄]₂CuCl₄ crystal with a new commensurate phase characterized by a dimensionless wavenumber q = 2/5 is constructed on a plane specified by two coefficients of the thermodynamic potential. This diagram is used as the basis for the construction of a theoretical pressure-temperature (P-T) phase diagram. The theoretical P-T phase diagram thus obtained is compared with the experimental P-T phase diagram.     

Electric field-induced formation of a new commensurate phase of the [N(CH<Subscript>3</Subscript>)<Subscript>4</Subscript>]<Subscript>2</Subscript>CuCl<Subscript>4</Subscript> crystal

The formation of a new commensurate phase with a dimensionless wave number q = 1/3 in an [N(CH₃)₄]₂CuCl₄ crystal under the action of an external electric field is analyzed theoretically. The phase diagram is constructed on a plane specified by two coefficients of the thermodynamic potential in the presence and in the absence of an external electric field.     

Optical transmission coefficient of crystalline [N(CH<Subscript>3</Subscript>)<Subscript>4</Subscript>]<Subscript>2</Subscript>MeCl<Subscript>4</Subscript> in the incommensurate phase

This a study of the optical transmission of [N(CH₃)₄]₂ZnCl₄ and [N(CH₃)₄]₂CuCl₄ crystals in the incommensurate phase when a defect density wave is present. It is found that an anomalous reduction in the transmission coefficient is caused by scattering of light owing to a realignment of the superstructure during transitions between metastable states. When a defect density wave is present, the anomalous optical transmission of the crystal is related to the scattering of light on superstructure inhomogeneities produced by a superposition of existing modulation waves.     

X-ray study of [N(CH<Subscript>3</Subscript>)<Subscript>4</Subscript>]<Subscript>2</Subscript>ZnCl<Subscript>4</Subscript> at low temperatures

The unit cell parameters a, b, and c of [N(CH₃)₄]₂ZnCl₄ have been measured by x-ray diffraction in the temperature range 80–293 K. Temperature dependences of the thermal expansion coefficients α_a, α_b, and α_c along the principal crystallographic axes and of the unit cell thermal expansion coefficient α_V were determined. It is shown that the a=f(T), b=f(T), and c=f(T) curves exhibit anomalies in the form of jumps at phase transition temperatures T₁=161 K and T₂=181 K and that the phase transition occurring at T₃=276 K manifests itself in the a=f(T) and b=f(T) curves as a break. A slight anisotropy in the coefficient of thermal expansion of the crystal was revealed. The phase transitions occurring at T₁=161 K and T₂=181 K in [N(CH₃)₄]₂ZnCl₄ were established to be first-order.     

Electrical characterization of the [N(CH<Subscript>3</Subscript>)<Subscript>4</Subscript>][N(C<Subscript>2</Subscript>H<Subscript>5</Subscript>)<Subscript>4</Subscript>]ZnCl<Subscript>4</Subscript> compound

The [N(CH₃)₄][N(C₂H₅)₄]ZnCl₄ compound has been synthesized by a solution-based chemical method. The X-ray diffraction study at room temperature revealed an orthorhombic system with P2₁2₁2 space group. The complex impedance has been investigated in the temperature and frequency ranges 420–520 K and 200 Hz–5 MHz, respectively. The grain interior and grain boundary contribution to the electrical response in the material have been identified. Dielectric data were analyzed using the complex electrical modulus M ^* for the sample at various temperature. The modulus plots can be characterized by full width at half height or in terms of a non-exponential decay function ϕ(t) = exp[(−t/τ) ^β ]. The detailed conductivity study indicated that the electrical conduction in the material is a thermally activated process. The variation of the AC conductivity with frequency at different temperatures obeys the Almond and West universal law.     

Manifestations of Phase Transitions and the Thermooptical-Memory Effect in the Absorption Spectra of (N(CH<Subscript>3</Subscript>)<Subscript>4</Subscript>)<Subscript>2</Subscript>CuCl<Subscript>4</Subscript> Crystals

The manifestations of phase transitions and the spatial modulation of the structure of the (N(CH₃)₄)₂CuCl₄ crystal in its absorption spectra have been investigated. It has been established that the thermooptical-memory effect manifesting itself in the absorption spectra of this crystal entirely corresponds to the model of ordering of defects and impurities in a sample with a modulated structure. It is shown that, as a result of stabilization of the crystal studied in the incommensurate phase, its symmetry and the symmetry of the metal-halogen complex in it lower depending on the defect wave. This manifests itself as a marked shift of the intraionic-absorption bands and an increase in their intensity. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 72, No. 3, pp. 386–390, May–June, 2005.     

Signs of phase transitions and a thermooptic memory effect in absorption spectra of (N(CH<Subscript>3</Subscript>)<Subscript>4</Subscript>)<Subscript>2</Subscript>Zn<Subscript>0.8</Subscript>Ni<Subscript>0.2</Subscript>Cl<Subscript>4</Subscript> solid solutions

We have studied the signs of phase transitions and spatial modulation of the structure in the absorption spectra of an (NCH₃)₄)₂Zn_0.8Ni_0.2Cl₄ crystal. We have observed the existence of phase transitions in the given solid solution at temperatures of 155 K, 168 K, 275 K, 280 K, and 296 K. We have established that the thermooptic memory effect observed in the absorption spectra is completely consistent with a model of defect ordering in the sample in the field of the modulated structure. According to this model, stabilization of the sample in an incommensurable phase leads to fixing of a certain symmetry in the crystal (usually a lower symmetry than the average symmetry of the incommensurable phase) and a metal-halogen complex corresponding to the defect wave. As a result, we observe an appreciable shift of the intra-ionic absorption bands and an increase in their intensity. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 75, No. 5, pp. 717–723, September–October, 2008.     

Crystallographic characteristics and phase transitions in the [N(C<Subscript>2</Subscript>H<Subscript>5</Subscript>)<Subscript>4</Subscript>]<Subscript>2</Subscript>CdBr<Subscript>4</Subscript> crystal in the low-temperature range

The results of x-ray structural studies of the [N(C₂H₅)₄]₂CdBr₄ crystal at low temperatures are presented. The unit cell parameters and the thermal expansion coefficients along the main crystallographic directions are measured at temperatures in the range from 90 to 320 K. The integrated intensities of the diffraction reflections are investigated as a function of the temperature. It is shown that the curves a = f(T), c = f(T), I ₅₀₀ = f(T), and I ₀₀₆ = f(T) at temperatures T ₁ ≈ 174 K and T ₂ ≈ 226 K exhibit anomalies in the form of abrupt changes in the lattice parameters and the diffraction reflection intensities. This indicates that the [N(C₂H₅)₄]₂CdBr₄ crystal undergo phase transitions at these temperatures. Moreover, there is an anomaly in the form of a small maximum at the temperature T ₃ = 293 K.     

Optical absorption spectra and magnetic phase transitions in TbFe<Subscript>3</Subscript>(BO<Subscript>3</Subscript>)<Subscript>4</Subscript>

Optical absorption spectra of the trigonal crystal of TbFe₃(BO₃)₄ in the vicinity of the ⁷F₆ → ⁵D₄ transition in a Tb³⁺ ion were studied as a function of temperature (2–70 K) and magnetic field strength (0–60 kOe) at 2 K. The splitting of the excited states of Tb³⁺ due to both the magnetic ordering of iron and an external magnetic field was determined. Abrupt splitting of the absorption lines of Tb³⁺ at temperature T_N of the magnetic ordering of the subsystem of iron was revealed, suggesting that the nature of such splitting is not entirely magnetic.     

Optical studies of phase transitions in the (NH<Subscript>4</Subscript>)<Subscript>3</Subscript>Ti(O<Subscript>2</Subscript>)F<Subscript>5</Subscript> crystal

Polarization-optical study of twinning and measurements of the Raman spectra and birefringence in oxyfluoride (NH₄)₃Ti(O₂)F₅ were carried out over the temperature range 90–350 K. Phase transitions were detected at temperatures T ₀₁ = 266 K (second-order transition) and T ₀₂ = 225 K (first order). It is assumed that the crystal symmetry is changed as follows: Fm3m ? I4/mmm ? I4/m. Anomalies of the spectral parameters are established in the frequency range of internal vibrations of ammonium ions and Ti(O₂)F₅ complexes. An analysis of the results shows that the transition at T ₀₁ is likely due to small shifts of the tetrahedral groups from their position on the triad axis and that the transition at T ₀₂ is due to fluorine-oxygen ordering of Ti(O₂)F₅ complexes.     

Cascade of phase transitions in GdFe<Subscript>3</Subscript>(BO<Subscript>3</Subscript>)<Subscript>4</Subscript>

Cascade of phase transitions in GdFe₃(BO₃)₄ at 156, 37, and 9 K has been detected by specific heat measurements and further studied by Raman scattering and Nd³⁺ spectroscopic probe method. A weakly first-order structural phase transition at 156 K is followed by a second-order antiferromagnetic ordering phase transition at 37 K and a first-order spin-reorientational phase transition at 9 K.     

Structural changes during phase transitions and the critical and noncritical order parameters in the (NH<Subscript>4</Subscript>)<Subscript>3</Subscript>Nb(O<Subscript>2</Subscript>)<Subscript>2</Subscript>F<Subscript>4</Subscript> crystal

The structures of two phases of the (NH₄)₃Nb(O₂)₂F₄ crystal, namely, the parent cubic phase and the most distorted low-temperature phase, have been determined from data of an X-ray diffraction experiment performed for a powder sample. The profile and structural parameters have been refined according to the procedure implemented in the DDM program. The results obtained have been discussed with invoking the group-theoretical analysis of the complete order parameter condensate, which takes into account the critical and noncritical atomic displacements and allows the interpretation of the obtained experimental data. It has been found that the most probable sequence of structural transformations occurring in the crystal can be schematically represented in the following form:

Nonlinear magnetic resonance in the (CH<Subscript>3</Subscript>NH<Subscript>3</Subscript>)<Subscript>2</Subscript>CuBr<Subscript>4</Subscript> crystal

The nonlinear microwave absorption in the (CH₃NH₃)₂CuBr₄ antiferromagnetic crystal is investigated experimentally. The temperature and angular dependences of the parameters of nonlinear resonance and the dependences of these parameters on the microwave pump power are analyzed. It is found that the nonlinear properties deteriorate with decreasing temperature and the linear and nonlinear contributions are competitive in character.     

Magnetic properties of the quasi-two-dimensional crystal (CH<Subscript>3</Subscript>NH<Subscript>3</Subscript>)<Subscript>2</Subscript>CuBr<Subscript>4</Subscript>

The magnetic properties of (CH₃NH₃)₂CuBr₄ quasi-two-dimensional crystals were studied experimentally. The magnetic-field and temperature dependences of magnetization were measured for various magnetic field orientations relative to the crystallographic axes. Possible reasons for features in the behavior of the magnetization are discussed.     

Structural Phase Transition of Perovskite-Type N(CH<Subscript>3</Subscript>)<Subscript>4</Subscript>CdBr<Subscript>3</Subscript> Studied by MAS NMR and Static NMR

The structural geometry change in the perovskite-type N(CH₃)₄CdBr₃ single crystal near the phase transition temperature of T _C = 390 K was investigated using magic angle spinning nuclear magnetic resonance techniques. For ¹H and ¹³C nuclei, the temperature dependences of their chemical shift, spectral intensity, and spin–lattice relaxation time (T _1ρ) in the rotating frame were obtained and analyzed. While the chemical shift and T _1ρ of ¹H showed change near T _C, those of ¹³C did not. In addition, the ¹¹³Cd spin–lattice relaxation time T ₁ in the laboratory frame near T _C show no evidence of anomalous change near the phase transition temperature, which coincides with the measured changes in the ¹H T _1ρ. The driving force for this phase transition was connected to the ¹H in the CH₃ groups.     

Features of the pressure-induced phase transitions in Eu<Subscript>2</Subscript>(MoO<Subscript>4</Subscript>)<Subscript>3</Subscript> single crystals

The structural changes induced by a 9-GPa pressure in Eu₂(MoO₄)₃ single crystals at room temperature have been studied using x-ray diffraction. It is established that a structural phase transition from the initial tetragonal phase to the new high-pressure tetragonal phase occurs rather than solid-phase amorphization that was observed previously in polycrystalline samples. The samples in the observed transition remain single-crystalline despite a significant difference (ΔV ～ 18%) between the specific volumes of the initial and final phases. It is shown that the transition from the initial state to the high-pressure phase occurs via the formation of broad transition zones featuring a continuous and smooth change of the crystal lattice parameters.     

Thermophysical studies of the phase transitions in (NH<Subscript>4</Subscript>)<Subscript>3</Subscript>NbOF<Subscript>6</Subscript> crystals

The thermophysical properties of oxyfluoride (NH₄)₃NbOF₆ were studied in detail over wide ranges of temperatures and pressures. At atmospheric pressure, a sequence of four structural phase transitions was established with the following changes in entropy: ΔS ₁ = Rln 2.7, δS ₂ = Rln38.3, ΔS ₃ = 0.08R, and ΔS ₄ = 0.17R. An external hydrostatic pressure was found to narrow the region of existence of the initial cubic phase. A triple point was detected in the p-T diagram; at a pressure above 0.07 GPa, the transition between the tetragonal and monoclinic phases occurs through a distorted high-pressure phase.     

Absorption and luminescence spectra of KHo(WO<Subscript>4</Subscript>)<Subscript>2</Subscript> and KEr(WO<Subscript>4</Subscript>)<Subscript>2</Subscript> single crystals

The optical absorption and luminescence properties of potassium-holmium and potassium-erbium double tungstates have been studied. It is established that the potassium-holmium double tungstate belongs to a group of biaxial and pleochromic crystals. The emission and excitation spectra of the KHo(WO₄)₂ and KEr(WO₄)₂ single crystals were measured at room temperature.Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 71, No. 6, pp. 810–814, November–December, 2004.This revised version was published online in April 2005 with a corrected cover date.     

Phase transitions in the oxyfluoride (NH<Subscript>4</Subscript>)<Subscript>3</Subscript>NbOF<Subscript>6</Subscript>

(NH₄)₃NbOF₆ single crystals were grown, polarization-optical studies were performed, and birefringence was measured over the temperature range 90–500 K. A sequence of first-order structural phase transitions was found at temperatures T _1↓ = 259.7 K and T _2↓ = 257.7 K with temperature hysteresis δT ₁ = 0.9 K and δT ₂ = 1.9 K. The transitions are accompanied by twinning and the following change in the crystal symmetry: cubic ? tetragonal ? monoclinic. Optical second harmonic generation is found to occur at room temperature, which indicates that the cubic phase is not centrosymmetric. It is assumed that the phase transitions are ferroelastic and ferroelectric in nature.