Effects of electron localization in V2 − y O3

The effect of nonstoichiometry on the metal-insulator phase transition in V₂O₃ is studied. It is established that an increase in the vanadium deficiency in V2 ? yO₃ brings about a shift in the phase transition temperature toward lower temperatures and an increase in the width of the temperature hysteresis loop of the electrical conductivity. As the vanadium deficiency increases to a level corresponding to the composition ～V_1.974O₃, the phase transition completely disappears and the sample remains metallic down to T = 1.6 K. The magnetoresistance is measured for samples of this composition in longitudinal and transverse magnetic fields at T = 4.2 K.     

Specific heat of the [NH<Subscript>2</Subscript>(CH<Subscript>3</Subscript>)<Subscript>2</Subscript>]<Subscript>2</Subscript>ZnCl<Subscript>4</Subscript> crystal in the temperature region 80–300 K

The specific heat of [NH₂(CH₃)₂]₂ZnCl₄ was measured calorimetrically in the temperature region 80–300 K. As the temperature T decreases, the C _p (T) dependence indicates a phase transition sequence, with the phase transition at T₆=151 K observed for the first time. The thermodynamic characteristics of the crystal were refined. The transformation occurring at T₂=298.3 K is shown to be an incommensurate-commensurate phase transition.     

Evidence for a spin-reorientation type phase transition in FeGeO3

Using single crystal susceptibility, Mössbauer and magnetoelectric measurements, the nature of the two low temperature phase transitions in the clinopyroxine metagermanate FeGeO₃ is studied. It is concluded that FeGeO₃ orders antiferromagnetically along the unique b axis at T_N = 47 ± 1°K and undergoes a spontaneous, second-order phase transition of the spin reorientation type at T_R = 17 ± 3°K. Only below T_R does FeGeO₃ exhibit magnetoelectricity.     

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.     

Acoustic properties of the disordered relaxor ferroelectric PbSc1/2Ta1/2O3

The behavior of acoustic phonons in crystals of a relaxor ferroelectric, namely, the lead scandium tantalate PbSc_1/2Ta_1/2O₃ (PST), is studied in the vicinity of the diffuse phase transition. The behavior of longitudinal and transverse acoustic phonons in a PST single crystal is examined using Brillouin scattering. The phonon subsystem is found to behave anomalously in the vicinity of T = 297 K, which can probably be assigned to the existence of a phase transition. Analysis of the results obtained yields the values of the elastic moduli C₁₁, C₁₂, and C₄₄ for the cubic phase of the crystal over a wide temperature range.     

Structural Phase Transition and the Dielectric Permittivity of the Model Lipid Bilayer [(CH2)12(NH3)2]CuCl4

Structural phase transitions in the lipid-like bilayer material [(CH₂)₁₂(NH₃)₂]CuCl₄ have been observed using differential thermal scanning. The compound shows an irreversible thermochromic transition at ? 465 K and three reversible transitions at T ₁ = 433 ± 4 K and T ₂ = 411 ± 2 K and T ₃ = 358 K. The transition at 350 K is ascribed to chain melting. The other two correspond to crystalline phase transformation.

Phase (IV) T₃ = 358 ± 2K Phase (III) T₂ = 411 ± 2K Phase (II) T₁ = 433 ± 4K Phase (I)

Dielectric permittivity is studied as a function of temperature in the range 300-440 K and frequency, range (60 Hz-100 kHz). It confirms the observed transitions. The dielectric permittivity reflects rotational and conformational transitions for the compound. The variation of the real part of the conductivity with temperature is thermally activated in the temperature range above 350 K, with frequency-dependent activation energy, the values of activation energy lie in the range of ionic hopping. The dependence of the conductivity on frequency follows the universal power law σ = σ₀ + A(T) ω ^{s ( T )} with 0<s<1. Comparison of this material with other members of the series is discussed     

X-ray diffraction investigation of the thermochromic phase transition in an [NH2(C2H5)2]2CuCl4 crystal

The unit cell parameters of an [NH₂(C₂H₅)₂]₂CuCl₄ crystal are determined using x-ray diffraction analysis, and the thermal expansion coefficients along the principal crystallographic directions are calculated in the temperature range 100–330 K. The behavior of the intensities of the diffraction reflections from the (100), (010), and (001) crystallographic planes is studied in the vicinity of the thermochromic phase transition temperature. The occurrence of a first-order phase transition in the [NH₂(C₂H₅)₂]₂CuCl₄ crystal at T ≈ 324 K is confirmed experimentally.     

Effect of γ-irradiation on the heat capacity of an [NH2(CH3)2]2 · CuCl4 crystal in the temperature range 80–300 K

The heat capacity of [NH₂(CH₃)₂]₂ · CuCl₄ crystals prior to and after γ-irradiation with doses of 1, 5, 10, and 50 MR is measured by the calorimetric method in the temperature range 80–300 K. It is found that, as the temperature decreases, the temperature dependence C _p (T) exhibits two anomalies which correspond to phase transitions from the incommensurate to the ferroelectric phase at T _c =281 K and from the ferroelectric to the ferroelastic phase at T ₁=255 K. The nature of the anomalies is typical of a first-order phase transition. In addition, a smeared anomaly in the form of a small increase in the heat capacity of the ferroelectric phase is observed at T≈275 K. It is demonstrated that when the dose of γ-irradiation increases, the anomalies decrease in magnitude and the phase transition temperatures are displaced: T _c increases and T ₁ decreases.     

Dielectric response of the relaxor ferroelectric Pb(Mg1/3Nb2/3)O3 in the nonergodic state after a DC electric field is turned off

The Pb(Mg_1/3Nb_2/3)O₃ (PMN) relaxor system is used as an example to analyze the temperature dependences of the low-frequency dielectric permitivity (?′(T)) measured during zero-field heating (ZFH) from T = 10 K to T = 300 K after using different field cooling (FC) conditions. No changes in the temperature dependences of the permittivity have been detected during the transition from a nonergodic relaxor state (NERS) into an ergodic relaxor state (ERS) (at T _f ≈ 216 K). However, the difference Δ?′(T) between the curves corresponding to different field cooling conditions in the same electric field has different shapes and different values below and above T → (T _f + 9 K)^? (for E _dc = 1.52 kV/cm). The reduced permittivities ?′_r(T, f) recorded under different cooling conditions are shown to change their behavior when passing through T = T _f + 9 K. In NERS, these curves diverge: the stronger the field (0 ≤ E _dc ≤ 3 kV/cm), the larger the divergence. In ERS, however, the ?′_r(T, f) curves coincide under different cooling conditions irrespective of the field. The character of the changes in Δ?′(T) and ?′_r (T, f) during the NERS-ERS transition is frequency-independent. The difference in the behavior of the dielectric response during ZFH after cooling in different (ZFC, FC) modes (even in a weak field), for both transition through T _f and cooling down to T = 10 K, indicates different NERSs forming under these conditions. The contribution to ?′(T) from slowly relaxing regions (ω ～ 0.1 mHz), whose polarization is reoriented after the field is turned off, is responsible for the fact that, during the NERS-ERS transition, the ?′_r(T, f) curves coincide at a temperature that is higher than T = T _f.     

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.     

Giant thermal hysteresis of sound velocity and internal friction in a La0.8Sr0.2MnO3 single crystal

Temperature dependences of the velocity of longitudinal sound V ₁ and the internal friction Q ^?1 are studied for a La_0.8Sr_0.2MnO₃ single crystal in the temperature range 5–350 K. The latter includes the temperature of the structural phase transition T _s ≈95 K (from the Pnma orthorhombic low-temperature phase to the $R\bar 3c$ rhombohedral high-temperature one) and the Curie point T _c =308 K. Near the temperatures T _s and T _c , the curves V ₁(T) and Q ^?1(T) exhibit pronounced singularities. Outside the vicinities of T _s and T _c , the velocity of sound monotonically decreases with increasing temperature. A thermal hysteresis of giant width is observed in the aforementioned dependences. The hysteresis is attributed to the following mechanism: when the crystal under study is heated starting at temperatures T<T _s , some regions occupied by the Pnma low-temperature phase are retained in the $R\bar 3c$ matrix up to the temperature T=350 K.     

Temperature Change in the Electronic Spectra of an NH2(CH3)2CuCl3 Crystal in Phase Transitions

Based on data of the spectral studies of an NH₂(CH₃)₂CuCl₃ crystal, the presence of phase transitions of the first kind at temperatures T ₁ = 282.5 K and T ₂ = 245 K (in a cooling regime) is confirmed. Identification of the intraionic absorption bands of the Cu²⁺ ion and calculation of the parameters of the energy and space structure of the crystal are carried out. A decrease in the tetragonal distortion of the CuCl₅ polyhedron with decreasing the temperature is found. The empirical Urbach rule is observed to be fulfilled in the lowtemperature phases of the crystal.     

DSC study of superionic phase transition in (NH4)4H2(SeO4)3 single crystals

DSC and complex impedance studies of the protonic conductor (NH₄)₄H₂(SeO₄)₃, which undergoes a superionic phase transition of first order at T_s = 378 K show that the activation energy of ionic conductivity d(lg σ)/dt and the ordering enthalpy ΔC_p of the crystal are proportional: d(lg σ)/dT = XΔC_p/RT_s + const, as found for MAg₄I₅ crystals undergoing a second-order superionic phase transition. Thus the short-range order environment of the species involved in fast-ion transport plays the main role in the superionic phase transition. This is also supported by the value of the entropy change at T_s, ΔS = 43 J/mole·K. A new metastable phase was found to be induced on heating the (NH₄)₄H₂(SeO₄)₃ crystal above T_s.     

EPR study of a new low-temperature phase transition in Zn(ClO4)2·6H2O

From a temperature variation EPR study of Mn²⁺ doped single crystals of Zn(ClO₄)₂·6H₂O phase transition has been detected at T₂~290 K. The phase relationships in this crystal are as follows. Phase I transforms atT₂~346K to Phase II, which in turn transforms to Phase III at T₂ ~ 290K. The latter exists down to at least 220 K. The space group symmetry of crystal may be the same, i.e. Pmn2₁ both above and below T₂. The water-perchlorate sublattice symmetry below T₂ is found to be lower than the P6₃mc symmetry determined previously by X-ray measurements. The onset of a monoclinic or lower symmetry distortion of the water octahedron around a metal ion which starts just below T₂, is reflected through the observed temperature dependence of the rhombic distortion parameter E. It is felt that during this phase transition a change in the degree of configurational disorder associated with the perchlorate tetrahedra takes place, which in turn modifies the hydrogen bonded interaction in the crystal and consequently results in the onset of temperature dependent displacements of the mean positions of the oxygens of the water molecules.     

Investigation of the ferroelastic phase transition in the SrMgF4 pyroelectric crystal

A SrMgF₄ compound has been synthesized and a high optical-quality crystal has been grown. Optical-polarization observations, X-ray diffraction analysis, and the measurement of the birefringence Δn _i (t) in the SrMgF₄ crystal have been carried out in the temperature range of 90–1200 K. A second-order improper ferroelastic phase transition accompanied by birefringence anomalies and the symmetry change P112₁ (Z = 12) ? Cmc2₁ (Z = 4) has been discovered at T ₀ = 478 ± 1 K. The crystal remains pyroelectric in both phases. Considerable contributions of the fluctuations of the order parameter have been observed in the temperature ranges of (T ₀ ? T) < 15 K and (T ? T ₀) < 60 K.     

Heat capacity of the [N(C<Subscript>2</Subscript>H<Subscript>5</Subscript>)<Subscript>4</Subscript>]<Subscript>2</Subscript>CdBr<Subscript>4</Subscript> crystal in the temperature range 80–300 K

The heat capacity of the [[N(C₂H₅)₄]₂CdBr₄ crystal is measured by the calorimetric method in the temperature range from 80 to 300 K. It is revealed for the first time that the temperature dependence of the heat capacity C _p (T) exhibits an anomaly associated with the first-order phase transition occurring at the temperature T ₁ = 226.5 K. A long relaxation of the temperature of the crystal is observed in the temperature range 150–165 K.     

Phase transition and triplet exciton mobility in anthracene—tetracyanobenzene charge-transfer single crystals

Triplet-Excitons in a mixed 1 : 1 anthracene—tetracyanobenzene single crystal are established by ESR-spectrocopy. These excitons (lifetime 0.5 msec) are characterized by a hopping frequency of v = 1.3 × 10⁶ K at 300K. The temperature dependence of the ESR line shape indicates a phase transition of the crystal at T_t = 205K. Above and below the phase transition the exciton mobility is nearly temperature independent.     

Br NQR relaxation and successive phase transitions of CH3NH3HgBr3

The measurement of ⁸¹Br NQR in CH₃NH₃HgBr₃ has been carried out in the temperature range between 80 and 300 K using a pulse NQR method. The temperature dependence of ⁸¹Br NQR frequencies in CH₃NH₃HgBr₃ has revealed that it undergoes three characteristic successive phase transitions at T?=?123, 184 and 239 K. The phase transition temperature at T?=?239 K is the second-order type, whereas those at T?=?184 and 123 K are the first-order nature of the phase transitions. Each phase transition seems to be closely related to the motions of methyl ammonium cation as a partial or whole. The enhancement of 1/T ₁ at T?=?239 K indicates the onset of the molecular motion of the cation as a whole with increasing temperatures.     

Crystal structure and structural transition caused by charge-transfer phase transition for iron mixed-valence complex (n-C3H7)4N[FeFe(dto)3] (dto=C2O2S2)

(n-C₃H₇)₄N[Fe^IIFe^III(dto)₃] shows a new type of first order phase transition called charge-transfer phase transition around 120 K, where the charge transfer between Fe^II and Fe^III occurs reversibly. Recently, we have succeeded in obtaining single crystals of the title complex and determined the crystal structure at room temperature. Crystal data: space group P6₃, Z=2. Moreover, we have investigated the structural transition caused by the charge-transfer phase transition by means of powder X-ray diffraction measurement. When the temperature is decreased, the a-axis, which corresponds to the hexagonal ring size in two-dimensional honeycomb network structure of [Fe^IIFe^III(dto)₃]_∞, contracts by 0.1 Å at the charge-transfer transition temperature (T_CT), while the c-axis, perpendicular to the honeycomb network layer, elongates by 0.1 Å at T_CT. Consequently, when the temperature is decreased, the unit cell volume decreases without noticeable anomaly around T_CT, which is responsible for the quite small vibrational contribution to the entropy change, compared with usual spin crossover transition. Thus, the charge-transfer phase transition around 120 K for (n-C₃H₇)₄N[Fe^IIFe^III(dto)₃] is regarded as spin entropy driven phase transition.     

Pressure-induced structural phase transition in ReO3

We have investigated the pressure-induced structural phase transition in ReO₃ by neutron diffraction on a single crystal. We collected neutron diffraction intensities from the ambient and high pressure phases at P=7 kbar and refined the crystal structures. We have determined the stability of the high pressure phase as a function temperature down to T=2 K and have constructed the (P-T) phase diagram. The critical pressure is P_c=5.2 kbar at T=300 K and decreases almost linearly with decreasing temperature to become P_c=2.5 kbar at T=50 K. The phase transition is driven by the softening of the M₃ phonon mode. The high pressure phase is formed by the rigid rotation of almost undistorted ReO₆ octahedra and the Re-O-Re angle deviates from 180°. We do not see any evidence for the existence of the tetragonal (P4/mbm) intermediate pressure phase reported earlier.