Phase transition effects in polycrystalline Hg<Subscript>2</Subscript>Br<Subscript>2</Subscript> samples

The effects accompanying the ferroelastic phase transition in Hg₂Br₂ polycrystalline samples are compared in an x-ray diffraction study with similar effects observed to occur in Hg₂Br₂ single crystals. In particular, an analysis is made of the “orthorhombic” splitting of the basal plane reflections and the behavior with temperature of the Bragg and diffuse reflections from the X points of the Brillouin zone, which characterize the behavior of the order parameter and its fluctuations, respectively. Polycrystalline samples exhibit strong smearing of the phase transition effects originating from the existence of damaged surface layers and elastic and plastic strain fields which induce order parameter fluctuations over a wide temperature range.     

Excitons and energy transfer in KPb<Subscript>2</Subscript>Cl<Subscript>5</Subscript> and RbPb<Subscript>2</Subscript>Br<Subscript>5</Subscript> laser crystals

Excitonic states, radiative relaxation of electronic excitations, and energy transfer to luminescence centers in both undoped and rare-earth activated (Pr, Er, Nd, Ho, Tb, Tm) KPb₂Cl₅ and RbPb₂Br₅ crystals were studied using low-temperature (8 K) time-resolved VUV spectroscopy under selective photoexcitation by synchrotron radiation.     

High-frequency EPR of Tb<Superscript>3+</Superscript>-doped KPb<Subscript>2</Subscript>Cl<Subscript>5</Subscript> crystal

High-frequency electron paramagnetic resonance (EPR) spectra of the KPb₂Cl₅:Tb³⁺ crystal have been investigated. Three types of spectra were observed in the frequency range of 74–200 GHz. The most intensive spectrum with the resolved hyperfine structure corresponded to transitions between sublevels of the¹⁵⁹Tb³⁺ ground quasi-doublet with the zero-field splitting (ZFS) close to 48 GHz. Experimental results were analyzed by the exchange charge model of the crystal field affecting terbium ions in low-symmetry Pb²⁺ positions with the chlorine sevenfold coordination and the charge compensating vacancy in the nearest potassium site. The calculated values ofg-factors and ZFS were in agreement with the experimental data. The nature of a broad EPR line with ZFS of about 180 GHz and of additional weak EPR lines observed as satellites of the main Tb³⁺ lines was discussed.     

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.     

Vibrational spectrum and elastic properties of KPb<Subscript>2</Subscript>Cl<Subscript>5</Subscript> crystals

The Raman spectra and elastic moduli of KPb₂Cl₅ crystals were studied experimentally. The results are interpreted using a parameter-free model of the crystal lattice dynamics with inclusion of the multipole moments of the electron shells of ions. The calculated and experimental results are in good agreement. It is shown that not only the halogen ions but also the heavy cations make a significant contribution to the eigenvectors of high-frequency lattice vibration modes, which accounts for the relatively low frequencies of these modes.     

Transient optical absorption induced by an electron pulse in KPb<Subscript>2</Subscript>Cl<Subscript>5</Subscript> crystals

The efficiency of formation and time evolution of radiation-induced structural defects and pulsed luminescence in KPb₂Cl₅ crystals under the action of a single electron pulse (E = 250 keV, τ = 20 ns) have been investigated. The spectra (1.1–3.8 eV) and relaxation kinetics (time interval 5 × 10^?8?5 s) of transient optical absorption and the pulsed cathodoluminescence spectra and decay kinetics (1.4–3.1 eV) have been measured in the temperature range 80–300 K. It is revealed that the induced optical density and its time evolution depend strongly on temperature, and the absorption relaxation time contains several components and reaches several seconds at T = 300 K. The decay kinetics of transient absorption and pulsed cathodoluminescence kinetics have different orders and are controlled by different relaxation processes.     

Order parameter and its fluctuations in Hg<Subscript>2</Subscript>Br<Subscript>2</Subscript> model ferroelastics

The Bragg and diffuse reflections from different X points of the Brillouin zone boundary of the Hg₂Br₂ crystal in the paraphase are studied. The intensities of these reflections are related to the order parameter and its fluctuations. The temperature dependence of the order parameter and its fluctuations is analyzed, and the values of the critical exponents indicating closeness of the phase transition in these crystals to the tricritical point are determined.     

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.     

Phase transition in CdHfO<Subscript>3</Subscript>

The phase transition from an orthorhombic phase (space group Pnma) to a rhombohedral phase (space group R3m) of the CdHfO₃ hafnate is investigated using methods of structural analysis. It is shown that crystal lattices of both phases contain polar structural units (octahedra, cubooctahedra). On this basis, it is assumed that the orthorhombic and rhombohedral phases of the CdHfO₃ compound are the antiferroelectric and ferroelectric phases, respectively.     

Phase transition in YbAl<Subscript>3</Subscript>C<Subscript>3</Subscript>

¹⁷⁰Yb M?ssbauer spectroscopy, temperature dependent X-ray, magnetisation and specific heat data are presented in the hexagonal intermetallic YbAl₃C₃, in order to shed light on the isostructural transition occurring near 80 K and to investigate the electronic state of the Yb ion above and below the transition. In the low temperature phase, we find that there occurs an atomic rearrangement in the hexagonal unit cell, leading to a strong symmetry lowering at the Yb site. We show that no magnetic ordering of the Yb³⁺ moments occurs down to 0.04 K, and we discuss this finding in terms of 4f-conduction electron hybridisation and geometric frustration.     

Synthesis and electrical conductivity of a new Ag<Subscript>6</Subscript>SnS<Subscript>4</Subscript>Br<Subscript>2</Subscript> superionic compound

The conditions of synthesizing a new Ag₆SnS₄Br₂ compound were studied. The crystallographic parameters of the unit cell were determined as follows: space group Pnma, a=6.67050(10) Å, b=7.82095(9) Å, c=23.1404(3) Å, and Z=4. The total electrical conductivity and its ionic component were measured by a dc probe method in the temperature range 210–380 K. Kinks in the conductivity curve and the differential thermogram of heating the alloy were revealed at 235 K. It was concluded that the mass and charge transfers in the compacted Ag₆SnS₄Br₂ alloy powder have an intragrain character.     

Ion-pair states of I<Subscript>2</Subscript>, Br<Subscript>2</Subscript>, IBr,and ICl

The experimentally determined energies and rotational constants of the vibrational levels v = 0–20 of the Ion-Pair states Ω = 0⁺, Ω = 1 of the I₂, Br₂, IBr, and ICl molecules are modeled. The model used includes three diabatic states, which correlate to X⁺(3P, 1D) + Y^～(1S₀). These states are coupled by the spin-orbit interaction, which is assumed to be independent of the internuclear distance. For IBr and ICl, as well as for the ungerade states of I₂ and Br₂, satisfactory results are obtained. The model is less applicable to the gerade states of I₂ and Br₂, which is possibly results from the retainment of the asymptotic J _A J _B coupling of the angular momenta at equilibrium internuclear distances.     

Phase transitions in the (NH<Subscript>4</Subscript>)<Subscript>2</Subscript>NbOF<Subscript>5</Subscript> oxyfluoride

The thermal and dielectric properties of the (NH₄)₂NbOF₅ oxyfluoride have been investigated. It has been established that the structural phase transitions Cmc2₁ → C2 → Ia observed at the temperatures T ₁ = 258.0 K and T ₂ = 218.9 K exhibit a nonferroelectric nature. The hydrostatic pressure, which stabilizes the initial phase and destabilizes the low-temperature phase, hardly affects the temperature range of stability of the intermediate phase. The model of sequential ordering of the structural elements due to phase transitions has been analyzed using experimental data on the entropies of the phase transitions.     

Phase separation in a manganite La<Subscript>0.95</Subscript>Ba<Subscript>0.05</Subscript>MnO<Subscript>3</Subscript> crystal

The structure and magnetic states of a crystal of lightly doped manganite La_0.95Ba_0.05MnO₃ were studied using thermal-neutron diffraction, magnetic measurements, and electrical resistance data in a wide temperature range. It is shown that, in terms of its magnetic properties, the orthorhombic crystal is characterized by two order parameters, namely, antiferromagnetic (T _N = 123.6 K) and ferromagnetic (T _C = 136.7 K). The results obtained differ in detail from known information on the manganites La_0.95Ca_0.05MnO₃ and La_0.94Sr_0.06MnO₃. Two models of the magnetic state of the La_0.95Ba_0.05MnO₃ crystal are discussed, one of which is a model of a canted antiferromagnetic spin system and another is associated with the phase separation of the manganite. Arguments are advanced in favor of the coexistence in this crystal of the antiferromagnetic phase (about 87%) with a Mn⁴⁺ ion concentration of 0.048 and the 1/16-type charge-ordered ferromagnetic phase (about 13%) with a Mn⁴⁺ ion concentration of 0.0625. The specific features of the manganite studied are due to self-organization of the La_0.95Ba_0.05MnO₃ crystal lattice caused by the relatively large barium ion size.     

Phase transition in nanostructured LaMnO<Subscript>3</Subscript>

Nanocrystalline LaMnO₃ samples have been synthesized by the coprecipitation of lanthanum and manganese salt solutions followed by annealing at 800°C in air and then in an argon flow. With the use of X-ray and neutron diffraction analysis, it has been found that the resulting samples had an orthorhombic crystal structure (space group Pbnm). In the nanocrystalline LaMnO₃ samples, an order-disorder phase transition from the low-temperature phase to the high-temperature phase occurs at (220 ± 10)°C, which is much lower than the value of 477°C for bulk LaMnO₃. The phase transition is due to the removal of the Jahn-Teller distortion of the Mn³⁺O₆ oxygen octahedrons and is accompanied by a decrease in the unit cell volume of lanthanum manganite over a narrow temperature range.     

Phase behaviour and superionic phase transition in K<Subscript>3</Subscript>H(SeO<Subscript>4</Subscript>)<Subscript>2</Subscript>

The phase behaviour of K₃H(SeO₄)₂ (TKHSe) above room temperature has been studied by differential scanning calorimetric (DSC), thermogravimetric analysis (TGA), simultaneous thermogravimetric and mass spectroscopy analysis (TG-MS), impedance spectroscopy (IS) and X-ray powder diffraction (XRD). Our results show that the previously claimed superionic phase transition in TKHSe at around 388 K (114.85 °C) is also the onset temperature of a slow thermal dehydration that occurs at reaction sites distributed over the surface of the crystal. That is, we propose that the TKHSe undergoes simultaneously a superionic phase transition and a decomposition process with a very slow reaction rate that is evident when the sample is pulverized to fine powder, both starting at the same temperature. As a matter of fact, we observe a decrease of the magnitude of the dc-conductivity on successive thermal runs in powdered sample attributed to sample decomposition that starts at the surface of the TKHSe grains, but the jump in conductivity is only a consequence of the order–disorder transition in the TKHSe phase that remains inside the grains.     

Field-induced magnetic transition in a mixed rare-earth aluminum garnet Er<Subscript>2</Subscript>HoAl<Subscript>5</Subscript>O<Subscript>12</Subscript>

The temperature dependence of the ac magnetic susceptibility of a single-crystal mixed rare-earth garnet Er₂HoAl₅O₁₂ has been investigated within the range from 1.8 to 300 K in a zero constant field and in applied bias fields of up to 9 T. In the absence of a constant magnetic field the magnetic susceptibility followed the Curie–Weiss law. The application of a constant magnetic field caused a magnetic phase transition, the temperature of which increased with increasing magnetic field. The temperature of the maximum of the ac magnetic susceptibility, which is a characteristic of the phase transition, did not show a noticeable dependence on the frequency of the alternating magnetic field.     

Supersensitive electronic transition in impurity Nd-Nd nanoclusters in CaF<Subscript>2</Subscript> crystal

A comparison of the theoretical calculations with the results of experiments on high-resolution laser spectroscopy made it possible to reveal the fine structure that arises in the supersensitive ⁴I_9/2? ⁴G_5/2 transition as a result of a strong coherent interaction in the Nd³⁺ ion pair in the CaF₂ crystal and construct the level splitting diagram for the ground and excited states of impurity Nd-Nd nanoclusters.     

Phase transition in Bi<Subscript>8</Subscript>Fe<Subscript>6</Subscript>Ti<Subscript>3</Subscript>O<Subscript>27</Subscript> multiferroic ceramics

The polycrystalline Bi₈Fe₆Ti₃O₂₇ compound was prepared by a high-temperature solid-state reaction technique. Preliminary structural analysis by X-ray diffraction (XRD) confirms the formation of a single-phase compound in an orthorhombic crystal system at room temperature. The elemental content of the compound was analyzed by EDAX microanalysis. Microstructural analysis by scanning electron microscopy (SEM) shows that the compound has well defined grains, which are distributed uniformly throughout the surface of the pellet sample. Detailed studies of temperature-dependent dielectric response at various frequencies show dielectric anomalies at 380, 389 and 403°C for 10 kHz, 100 kHz, and 1 MHz respectively. The hysteresis loop observed by applying an electric field of 12 kV/cm on the poled sample with smaller remanent polarization supports the existence of ferroelectricity in this material. The value of d₃₃ of the compound was found to be 19 pC/N.