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.     

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.     

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.     

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:

Effect of deuteration on the thermal properties and structural parameters of the (NH<Subscript>4</Subscript>)<Subscript>2</Subscript>WO<Subscript>2</Subscript>F<Subscript>4</Subscript> oxyfluoride

The thermal properties and structure of (ND₄)₂WO₂F₄ crystals are investigated. It is established that deuteration does not lead to a change in the symmetry of the initial phase Cmcm but considerably decreases the extent of its disordering, which, in turn, brings about a substantial decrease in the phase transition entropy. Apart from the anomalies associated with phase transitions characteristic of the protonic compound, the heat capacity exhibits two additional anomalies. Analysis of the phase diagram of the deuterated crystal reveals a triple point at a pressure p = 0.18 GPa, which is predicted for (NH₄)₂WO₂F₄ at about 0.7 GPa.     

Phase transitions of SC(NH<Subscript>2</Subscript>)<Subscript>2</Subscript> ferroelectrics in Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-based nanoporous matrices

Temperature dependences of the linear permittivity ε' and the third harmonic amplitude γ_3ω of composites prepared by introducing ferroelectrics SC(NH₂)₂ into matrices of porous aluminum oxide Al₂O₃ with pore sizes 60 and 100 nm are determined. It is found that temperature T _c of the ferroelectric phase transition and the temperature T _i of the phase transition from incommensurable phase to the paraphrase increase significantly. The transition shifts increase as pore diameters decrease.     

Vibrational spectra of disordered oxyfluoride (NH<Subscript>4</Subscript>)<Subscript>3</Subscript>WO<Subscript>3</Subscript>F<Subscript>3</Subscript>

Comparative analysis of the IR absorption and Raman scattering spectra of a polycrystalline sample of perovskite-type oxyfluoride (NH₄)₃WO₃F₃ has been performed in the frequency range 370–4000 cm^?1 at temperatures from 92 to 303 K, including the transition between the orientationally disordered cubic and low-symmetry phases. The conformation of WO₃F₃ octahedral groups is established and transitional anomalies of the internal modes of these groups and ammonium ions are revealed. Comparative analysis of the IR and Raman spectra suggests that the phase transition under study is mainly related to the ordering of octahedral groups and formation of W-O…H-N hydrogen bonds.     

Refractometry of mechanically compressed (NH<Subscript>4</Subscript>)<Subscript>2</Subscript>SO<Subscript>4</Subscript> crystals

The effect of uniaxial mechanical pressure σ _m ≤ 150 bar on the spectral (300–800 nm) dependence of the birefringerence Δn _i and refractive indices n _i of (NH₄)₂SO₄ crystals has been investigated. It is shown that the dispersion of n _i (λ) and Δn _i (λ) is normal and sharply increases with approach to the absorption edge. It is established that uniaxial pressure does not change the character of the dispersions dn _i /dλ and dΔn _i /dλ and only affects their magnitudes. It is shown that the increase in the refractive indices under uniaxial stress is mainly due to the increase in the refraction caused by the increase in the band gap and long-wavelength shift of the UV absorption band maximum.     

Anomalous behavior of the velocity of hypersonic acoustic phonons in (NH<Subscript>4</Subscript>)<Subscript>3</Subscript> H(SO<Subscript>4</Subscript>)<Subscript>2</Subscript> crystals

The Gross-Pitaevski equation modified through the inclusion of a term accounting for the nonlocality of interatomic interaction was used to demonstrate the occurrence of extremely narrow two-and three-dimensional solitonic states in atomic Bose-Einstein condensates. The estimates of the sizes of these states gave a value of ～ 20–60 nm (atomic “needles” and “bullets”) for lithium atoms. The soliton lifetimes caused by two-and three-particle collisions were estimated. The limiting possibilities of the formation of nanostructures using needles and bullets were compared with the possibilities of other nanolithographic methods.     

Effect of uniaxial pressure on the infrared spectra of (NH<Subscript>4</Subscript>)<Subscript>2</Subscript>SO<Subscript>4</Subscript> crystals

The infrared reflectance spectra of a mechanically free or uniaxial-pressure-confined (NH₄)₂SO₄ crystal were studied for the first time in the spectral range 800–1700 cm^?1 in three crystallographic directions. Using the Kramers-Kronig relations, the dispersion and pressure dependences of the following quantities are obtained: the index of refraction n, the real (?₁) and imaginary (?₂) parts of the permittivity, the frequencies of longitudinal (ω_LO) and transverse (ω_TO) optical vibrations, the damping constant γ, and the oscillator strength f of the mechanically free or clamped (NH₄)₂SO₄ crystal. A considerable change in the main reflection bands with pressure was observed, which is due to the effect of uniaxial pressure on the NH₄ and SO₄ tetrahedral frames.     

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.     

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.     

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.     

Retardation of polarization in mixed K<Subscript>0.88</Subscript>(NH<Subscript>4</Subscript>)<Subscript>0.12</Subscript>H<Subscript>2</Subscript>PO<Subscript>4</Subscript> crystal

The time dependences of polarization of K_0.88(NH₄)_0.12H₂PO₄ mixed crystal have been studied within the temperature range of 74–100 K. Two mechanisms of polarization relaxation were found. The first mechanism is caused by domain walls lateral motion and their interaction with point lattice defects. The second one supposedly is due to polar regions infiltration through the regions of frustrated paraelectric phase.     

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.     

Phase transition in a NaBi(MoO<Subscript>4</Subscript>)<Subscript>2</Subscript> crystal: Acoustic investigations

This paper reports on the results of acoustic investigations of a NaBi(MoO₄)₂ crystal in the temperature range from 20 to 70°C. The temperature dependences of the velocity of longitudinal ultrasonic waves propagating along the crystallographic axes z and x are measured at a frequency of 4 MHz. The results obtained demonstrate that a structural phase transition occurs in the NaBi(MoO₄)₂ crystal at a temperature of 309 K. The experimental findings are consistent with the assumption that the observed phase transition is either a second-order ferroelastic transition or a first-order ferroelastic transition that is very close to being a second-order phase transition.     

A Phenomenological Model of Structural Phase Transitions in RbDy(Wo<Subscript>4</Subscript>)<Subscript>2</Subscript>

A phenomenological model of structural phase transitions in double rubidium–dysprosium tungstate is proposed. The model is constructed by equivariant catastrophe theory methods. The temperature dependence of the heat capacity near the phase transitions at temperatures T₁ = 9 K and T₂ = 4.9 K was calculated. Comparison with the experimental data shows a satisfactory qualitative agreement. In terms of the proposed model, the low-temperature phase transition can be interpreted as isomorphic.     

Electronic spectra and phase transitions in thin [N(CH<Subscript>3</Subscript>)<Subscript>4</Subscript>]<Subscript>2</Subscript>CuCl<Subscript>4</Subscript> microcrystals

Optical absorption spectra in thin [N(CH₃)₄]₂CuCl₄ crystals in the thickness range 10 μm ≤ d < 100 μm have been studied. Strengthening of the crystal field has been found with a decrease in the [N(CH₃)₄]₂CuCl₄ crystal size. The reasons for absorption band shifts in the visible region depending on the [N(CH₃)₄]₂CuCl₄ crystal thickness and the manifestation of a size effect in crystals with an incommensurate superstructure are discussed.     

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.