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.     

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.     

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.     

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.     

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.     

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.     

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.     

CsLa(WO<Subscript>4</Subscript>)<Subscript>2</Subscript>, a new SRS-active crystal

The discovery of stimulated Raman scattering (SRS) in a CsLa(WO₄)₂ crystal and the first results of studying its steady-state χ⁽³⁾-nonlinear generation within the visible wavelength range are reported. This result has imparted the status of a multifunctional crystal with laser (with generating Ln³⁺ ions) and SRS-potential to tetragonal cesium-lanthanum tungstate.     

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:

Superproton phase transition in a K<Subscript>3</Subscript>H(SO<Subscript>4</Subscript>)<Subscript>2</Subscript> crystal

The conductivity and heat capacity of tripotassium hydrogen trisulfate single crystals were studied. It was shown that these single crystals undergo a solid-solid phase transformation upon heating with the formation of new phases, and that their properties change considerably. Anomalies related to the sorption and desorption of water vapor were observed in the formed multiphase system. Such anomalies were observed for the first time in measurements of the true heat capacity.     

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.     

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.     

Magnetic-resonance and thermophysical studies of the magnetic phase diagram for a GdFe<Subscript>2.1</Subscript>Ga<Subscript>0.9</Subscript>(BO<Subscript>3</Subscript>)<Subscript>4</Subscript> single crystal

The antiferromagnetic resonance, heat capacity, magnetic properties, and magnetic phase diagram of a GdFe₃(BO₃)₄ crystal in which some of the iron ions were substituted by diamagnetic gallium ions have been investigated. It has been found that the Neél temperature upon diamagnetic substitution decreased to 17 K compared to 38 K in the unsubstituted crystal. The effective exchange and anisotropy fields for GdFe_2.1Ga_0.9(BO₃)₄ have been estimated from the field dependences of magnetization and resonance measurements. The magnetic phase diagram of the crystal has been constructed from magnetic and resonance measurements. In GdFe_2.1Ga_0.9(BO₃)₄, there is no spontaneous reorientation and, in the absence of a magnetic field, the crystal remains an easy-axis one in the entire domain of magnetic ordering. The critical field of the reorientation transition to an induced easy-plane state in a magnetic field along the trigonal axis has been found to increase compared to that in the unsubstituted crystal.     

High-resolution spectroscopy of HoFe<Subscript>3</Subscript>(BO<Subscript>3</Subscript>)<Subscript>4</Subscript> crystal: a study of phase transitions

The transmission spectra of HoFe₃(BO₃) multiferroic single crystals are studied by optical Fourier-transform spectroscopy at temperatures of 1.7–423 K in polarized light in the spectral range 500–10 000 cm^–1 with a resolution up to 0.1 cm^–1. A new first-order structural phase transition close to the second-order transition is recorded at T_c = 360 K by the appearance of a new phonon mode at 976 cm^–1. The reasons for considerable differences in T_c for different samples of holmium ferroborate are discussed. By temperature variations in the spectra of the f–f transitions in the Ho³⁺ ion, we studied two magnetic phase transitions, namely, magnetic ordering into an easy-plane structure as a second-order phase transition at T_N = 39 K and spin reorientation from the ab plane to the c axis as a first-order phase transition at T_SR = 4.7 ± 0.2 K. It is shown that erbium impurity in a concentration of 1 at % decreases the spin-reorientation transition temperature to T_SR = 4.0 K.     

Growth and magneto-optical properties of LiTb(MoO<Subscript>4</Subscript>)<Subscript>2</Subscript> crystal

Lithium terbium molybdate (LiTb(MoO₄)₂) single crystal was grown by the Czochralski method. The lattice parameters of the crystal were determined by X-ray diffraction analysis. The absorption coefficient and the Faraday rotation spectrum (B=1.07 T) were investigated at wavelengths of 400–1500 nm at room temperature. Verdet constants of LiTb(MoO₄)₂ crystal at 532-, 633- and 1064-nm wavelengths were measured by the extinction method. The results show that LiTb(MoO₄)₂ crystal has a larger magneto-optical figure of merit than that of terbium gallium garnet at wavelengths of 600–1500 nm.     

Growth and characterization of a LaCa<Subscript>4</Subscript>O(BO<Subscript>3</Subscript>)<Subscript>3</Subscript> crystal

The non-linear optical (NLO) crystal LaCa₄ O(BO₃)₃ (LaCOB ) has been grown by the Czochralski method. X-ray diffraction experiments show that LaCOB crystal possesses the space group Cm, and its unit cell constants have been measured to be a=0.8168(3) nm,b=1.6081(7) nm and c=0.3630(6) nm, with an angle =101.39°. The thermal properties of LaCOB have been studied; the specific heat of the crystal is 321.9 J/molK at 330 K, and the three principal coefficients of thermal expansion of the principal axes have been calculated from the measured data to be 5.61×10^-6 K^-1, 7.21×10^-6 K^-1 and 11.01×10^-6 K^-1, respectively. The transmission spectrum shows that LaCOB crystal has a wide transparency wavelength range, and may be used as a NLO crystal. PACS 81.10.Fq; 65.40.Ba; 65.40.De     

Synthesis,crystal structure,Hirshfeld surface analysis,and vibrational and DFT investigation of [C<Subscript>6</Subscript>H<Subscript>10</Subscript>(NH<Subscript>3</Subscript>)<Subscript>2</Subscript>]<Subscript>3</Subscript>CuBr<Subscript>4</Subscript>.3Br

Single crystal of a new organic–inorganic hybrid material [C₆H₁₀(NH₃)₂]₃CuBr₄.3Br was synthesized by the slow evaporation method at room temperature and characterized by X-ray diffraction, FTIR, Raman spectroscopy, UV–Vis, dielectric measurements, and Hirschfield surface analysis. The title compound crystallizes in trigonal system \( P\overline{3} \).The crystal packing is governed by the N-H…Br and non-classical C-H…Br hydrogen-bonding interactions between the 1, 2-diamoniumcyclohexane cations, the tetrahedral [CuBr₄]^3? anions, and the isolated ion Br^?. Theoretical calculations were performed using density functional theory (DFT) for studying the molecular structure, vibrational spectra, and optical properties of the investigated molecule in the ground state. The optimized geometrical parameters obtained by DFT calculations are in good agreement with single crystal XRD data. The optical properties were investigated by optical absorption and show two bands at 260 and 305 nm.