Low-temperature specific heat of the Rb<Subscript>2</Subscript>KScF<Subscript>6</Subscript> elpasolite

The specific heat of single-crystal Rb₂KScF₆ is measured using ac calorimetry in the range 4–280 K. The results are discussed in the context of a group-theoretical analysis of possible distortions of the elpasolite structure and of experimental data obtained earlier with an adiabatic calorimeter in a narrower temperature region.     

Structures of distorted phases and critical and noncritical atomic displacements of elpasolite Rb<Subscript>2</Subscript>KInF<Subscript>6</Subscript> during phase transitions

The structures of all three phases of the Rb₂KInF₆ crystal have been determined from the experimental X-ray diffraction data for the powder sample. The refinement of the profile and structural parameters has been carried out by the technique implemented in the DDM program, which minimizes the differences between the derivatives of the calculated and measured X-ray intensities over the entire profile of the X-ray diffraction pattern. The results obtained have been discussed using the group-theoretical analysis of the complete order-parameter condensate, which takes into account the critical and noncritical atomic displacements and permits the interpretation of the experimental data obtained previously. It has been reliably established that the sequence of changes in the symmetry during phase transitions in Rb₂KInF₆ can be represented as $ Fm\bar 3m\xrightarrow[{0,0,\phi }]{{11 - 9\left( {\Gamma _4^ + } \right)}}{{I114} \mathord{\left/ {\vphantom {{I114} {m\xrightarrow[{\left( {\psi ,\phi ,\phi } \right)}]{{11 - 9\left( {\Gamma _4^ + } \right) \oplus 10 - 3\left( {X_3^ + } \right)}}{{P12_1 } \mathord{\left/ {\vphantom {{P12_1 } {n1}}} \right. \kern-\nulldelimiterspace} {n1}}}}} \right. \kern-\nulldelimiterspace} {m\xrightarrow[{\left( {\psi ,\phi ,\phi } \right)}]{{11 - 9\left( {\Gamma _4^ + } \right) \oplus 10 - 3\left( {X_3^ + } \right)}}{{P12_1 } \mathord{\left/ {\vphantom {{P12_1 } {n1}}} \right. \kern-\nulldelimiterspace} {n1}}}} $ Fm\bar 3m\xrightarrow[{0,0,\phi }]{{11 - 9\left( {\Gamma _4^ + } \right)}}{{I114} \mathord{\left/ {\vphantom {{I114} {m\xrightarrow[{\left( {\psi ,\phi ,\phi } \right)}]{{11 - 9\left( {\Gamma _4^ + } \right) \oplus 10 - 3\left( {X_3^ + } \right)}}{{P12_1 } \mathord{\left/ {\vphantom {{P12_1 } {n1}}} \right. \kern-\nulldelimiterspace} {n1}}}}} \right. \kern-\nulldelimiterspace} {m\xrightarrow[{\left( {\psi ,\phi ,\phi } \right)}]{{11 - 9\left( {\Gamma _4^ + } \right) \oplus 10 - 3\left( {X_3^ + } \right)}}{{P12_1 } \mathord{\left/ {\vphantom {{P12_1 } {n1}}} \right. \kern-\nulldelimiterspace} {n1}}}} .     

Optical phonons in Rb<Subscript>2</Subscript>TeBr<Subscript>6</Subscript> and Cs<Subscript>2</Subscript>TeBr<Subscript>6</Subscript> crystals

Raman scattering in Rb₂TeBr₆ and Cs₂TeBr₆ crystals is studied. The phonon spectra of the crystals are calculated using the factor group method. The number of Raman-active modes, their symmetries, and selection rules are found. Observed Raman spectrum lines are identified with atomic vibration modes of the crystal.     

Raman scattering by Hg<Subscript>2</Subscript>F<Subscript>2</Subscript> polycrystals

The Raman spectra of Hg₂F₂ polycrystals are experimentally measured for the first time. The spectra of Hg₂F₂ are interpreted using X-ray diffraction analysis and group-theoretical treatment. The results obtained are discussed in comparison with the spectra of Hg₂Hal₂ crystals.     

Magnon satellite bands in the optical spectrum of antiferromagnetic Rb<Subscript>2</Subscript>MnCl<Subscript>4</Subscript>

The evolution of optical absorption in a two-dimensional antiferromagnet is investigated in the range of the transition ⁶A_1g → ⁴A_1g, ⁴E _g (⁴G) observed in manganese ions in an external magnetic field inducing noncollinearity of the magnetic structure. It is revealed that hot and cold satellites of the exciton-magnon bands appear in the optical absorption spectrum and then increase in intensity. The shapes of the magnon satellite bands corresponding to a two-dimensional magnetic structure are calculated. It is demonstrated that magnons at the inner points of the Brillouin zone appreciably contribute to the absorption. The zero-point magnetic oscillations play a decisive role in the absorption associated with the magnon decay at low temperatures.     

Low-frequency Raman scattering from CeO<Subscript>2</Subscript> nanoparticles

Raman scattering measurements were performed on CeO₂ nanoparticles at room temperature. Low-frequency modes are assigned to confined acoustic vibrations of spherical CeO₂ nanoparticles. Frequencies of these vibrational modes have been calculated in the elastic continuum approximation, which considers a nanoparticle as a homogeneous elastic sphere. We assumed stress-free boundary conditions. The specific dependence of the vibrational frequency on the particle diameter enables the determination of the particle size from the experimental Raman frequency. The particle size value calculated in this way agrees well with the value acquired from the phonon confinement model. PACS 61.46.Df; 73.63.Bd; 63.22.+m     

The influence of phase transitions in the Rb<Subscript>2</Subscript>CdI<Subscript>4</Subscript> ferroelastic on the exciton absorption spectrum

The parameters of the long-wavelength exciton band for Rb₂CdI₄ films are investigated in the temperature range 90–410 K. It is found that the Rb₂CdI₄ films undergo a sequence of phase transitions at temperatures T_c1=380 K (paraphase → incommensurate phase), T_c2=290 K (incommensurate phase → ferroelastic phase I), and T_c3 = 210 K (ferroelastic phase I → ferroelastic phase II). The parameters of the exciton band (such as the spectral position and the half-width) measured during heating and cooling of the Rb₂CdI₄ film differ significantly. This is especially true for the incommensurate phase. Upon heating of the incommensurate phase, the domain boundaries become frozen, whereas the cooling of this phase is accompanied by the generation of solitons and their pinning, which, in turn, results in a first-order phase transition at the temperature T_c2. It is revealed that the oscillator strength of the exciton band anomalously increases in the range of existence of commensurate phase I (T_c3<-T<-T_c2) due to ordering of the Rb₂CdI₄ crystal lattice.     

Kinetics of Rb<Stack><Subscript>2</Subscript><Superscript>+</Superscript></Stack> and Rb<Superscript>+</Superscript> formation in laser-excited rubidium vapor

We have studied the formation of the molecular ion Rb₂⁺ and the atomic ion Rb⁺. These are created in laser excited rubidium vapor at the first resonance, 5s–5p and 5p-nl transitions. A theoretical model is applied to this interaction to explain the time evolution and the laser-power dependence of the population density of Rb⁺ and Rb₂⁺. A set of rate equations which describe: the temporal variation of the population density of the excited states; the atomic ion density; and the electron density, were solved numerically under the experimental conditions of Barbier and Cheret. In their experiment the Rb concentration was 1×10¹³cm⁻³ and the laser power was taken to be 50–500 mW at vapor temperature = 450 K. The results showed that the main processes for producing Rb₂⁺ are associative ionization and Hornbeck-Molnar ionization. The calculations have also showed that, the atomic ions Rb⁺ are formed through the Penning Ionization (PI) and photoionization processes. Moreover, a reasonable agreement between the experimental results and our calculations for the ion currents of the Rb⁺ and Rb₂⁺ is obtained.      

UV absorption spectra of thin films of Cs<Subscript>2</Subscript>CdI<Subscript>4</Subscript> and Rb<Subscript>2</Subscript>CdI<Subscript>4</Subscript> ferroelectrics

Thin films of M₂CdI₄ ferroelectrics (M=Cs, Rb) of orthorhombic structure were synthesized, and their electronic optical spectrum was studied. It was established that both compounds belong to direct-gap dielectrics and that their low-frequency excitons are localized on a sublattice made up of (CdI₄)^2? tetrahedra. The temperature dependence of the exciton band parameters was studied for Cs₂CdI₄ within the temperature interval 90–420 K. The phase transitions occurring in this interval manifest themselves as breaks in the temperature behavior of the band spectral positions and weak peaks in the halfwidth and oscillator strength.     

Electronic Raman scattering and the renormalization of the electron spectrum in LuB<Subscript>12</Subscript>

The electronic Raman scattering in LuB₁₂ single crystals of various isotope compositions is studied in the temperature range 10–650 K. The shape and the energy position of spectral maxima depend on the direction and magnitude of a probe wavevector, the temperature, and the excitation symmetry and remain unchanged when the isotope composition changes. Experimental spectra are compared with the spectra simulated on the basis of a calculated electronic structure. The experimental results are successfully described when the electron spectrum renormalization effects caused by electron–phonon coupling are taken into account. This confirms that the origin of the observed spectra in LuB₁₂ is due to Raman scattering by electrons. A comparison of the calculated and experimental data makes it possible to determine the coupling constant (λ_ep = 0.32) that gives the correct superconducting transition temperature.     

Exciton absorption spectra of Cs<Subscript>2</Subscript>CdI<Subscript>4</Subscript> and Rb<Subscript>2</Subscript>CdI<Subscript>4</Subscript> ferroelastic solid solutions

The exciton absorption spectra of thin films of (Cs_{1 − x} Rb _x )₂CdI₄ solid solutions have been investigated and the refractive index n(λ) in their transparency window in the concentration range of 0 ≤ x ≤ 1 has been measured. The exciton-band parameters and optical permittivity ɛ_∞(x) have been found to linearly depend on the concentration. It is established that excitons are incorporated into the CdI₂ sublattice of the solid solutions and belong to intermediate-coupling ones. The characteristics of excitons in ferroelastics are compared with the corresponding parameters for CdI₂, RbI, and CsI, which are used as components to synthesize ternary compounds.     

First- and second-order Raman scattering from MoTe<Subscript>2</Subscript> single crystal

We report on Raman experiments performed on a MoTe₂ single crystal. The system belongs to the wide family of transition metal dichalcogenides which includes several of the most interesting two-dimensional materials for both basic and applied physics. Measurements were performed in the standard basal plane configuration, by placing the ab plane of the crystal perpendicular to the wave vector k _i of the incident beam to explore the in-plane vibrational modes, and in the edge plane configuration with k _i perpendicular to the crystal c axis, thus mainly exciting out-of-plane modes. For both configurations we performed a polarization-dependent study of the first-order Raman components and detailed computation of the corresponding selection rules. We were thus able to provide a complete assignment of the observed first-order Raman peaks, in agreement with previous literature results. A thorough analysis of the second-order Raman bands, as observed in both basal and edge plane configurations, provides new information and allows a precise assignment of these spectral structures. In particular, we have observed and assigned Raman active modes of the M point of the Brillouin zone previously predicted by ab initio calculations but never previously measured.     

Thermodynamic properties and structure of oxyfluorides Rb<Subscript>2</Subscript>KMoO<Subscript>3</Subscript>F<Subscript>3</Subscript> and K<Subscript>2</Subscript>NaMoO<Subscript>3</Subscript>F<Subscript>3</Subscript>

According to the results of calorimetric and structural studies, the Fm{ie1202-1}m phase in K₂NaMoO₃F₃ remains stable at least to 100 K. No ferroelectric transformation assumed earlier has been revealed in a series of Rb₂KMoO₃F₃ samples prepared using various technologies. Only a phase transition of nonferroelectric origin has been observed near 195 K, and its thermodynamic characteristics have been determined. An analysis of the stability of the cubic structure of molybdenum fluorine-oxygen elpasolites-cryolites has been performed in the framework of the hypothesis on strengths of interatomic bonds. The barocaloric effect in Rb₂KMoO₃F₃ has been estimated.     

Superconductivity and spectroscopy of heterofullerides Rb<Subscript>2</Subscript>MC<Subscript>60</Subscript>, K<Subscript>2</Subscript>MC<Subscript>60</Subscript>, and KM<Subscript>2</Subscript>C<Subscript>60</Subscript> (M = Mg,Be)

A series of new heterofullerides with compositions Rb₂MC₆₀, K₂MC₆₀, and KM₂C₆₀ (M = Mg, Be) have been synthesized. Measurements of the temperature dependences of the magnetic susceptibility in the temperature interval from 4.2 to 300 K reveal a superconducting transition in heterofullerides K₂MgC₆₀, KMg₂C₆₀, K₂BeC₆₀, and Rb₂BeC₆₀ at temperatures T _c = 13–22 K. The electron states with uncompensated spin are studied by the electron paramagnetic resonance technique. The contributions of conduction electrons and localized electrons to the paramagnetic susceptibility are extracted.     

Raman scattering spectroscopy of inclusions of carbon in Al<Subscript>2</Subscript>O<Subscript>3</Subscript> films and its solid solutions with HfO<Subscript>2</Subscript>

We apply Raman scattering spectroscopy to study the nature of carbon inclusions in Al₂O₃ and (HfO₂) _x (Al₂O₃)_{1 ? x} films deposited using volatile complex compounds. Raman spectra of the films under investigation contain D and G vibrational modes, which indicate that carbon clusters of the sp ² configuration tend to form in the films. We estimate the size of clusters from the integrated intensity ratio I _D /I _G and find it to be in the range of 14–20 Å. The content of hydrogen in carbon clusters is calculated from the height of the photoluminescence pedestal and is found to vary from 14 to 30 at % depending on the regime of the film’s synthesis.     

Vibrational modes of acid hydrogen in CsH<Subscript>5</Subscript>(PO<Subscript>4</Subscript>)<Subscript>2</Subscript> and NaH<Subscript>5</Subscript>P<Subscript>2</Subscript>O<Subscript>6</Subscript>: inelastic neutron scattering

The vibrational modes of hydrogen bonds in CsH₅(PO₄)₂ and NaH₅P₂O₆ compounds are analyzed via inelastic incoherent neutron scattering in a wide range of temperatures and Raman light scattering at room temperature. The energy ranges have been determined for the γ, jg, and ? bands of the vibrational modes of acid hydrogens of these compounds. The dependences of the energy on the length of hydrogen bonds in CsH₅(PO₄)₂ have been revealed.     

Raman scattering in ZrB<Subscript>12</Subscript> cage glass

High-precision measurements of the Hall effect and Raman scattering have been performed for single crystals of ZrB₁₂ superconductor in the wide temperature range of 5–300 K. For ZrB₁₂, the boson peak with ω_max ~ 100 cm^–1 has been observed for the first time within the low-frequency range of the Raman spectrum I(ω). The sizes of vibrational clusters with the correlation length ranging from 25 to 35 Å are estimated. The relation between the renormalization of the low-frequency density of vibrational states accompanying the transition to the cage-glass phase (T* ~ 90 K) and the enhancement of superconductivity in ZrB₁₂ is discussed.     

Lattice dynamics and baric behavior of phonons in Hg<Subscript>2</Subscript>Cl<Subscript>2</Subscript> crystals at high hydrostatic pressures

A theoretical model based on long-range dispersion corrections of the charge density functional is proposed for model Hg₂Cl₂ calomel crystals, typical representatives of molecular inorganic compounds where the intermolecular interaction is found to play an important role. This model successfully describes the electronic state and the phonon spectrum of the above crystal, predicts the earlier unstudied phase transition at high hydrostatic pressure. Study of the baric behavior of the phonon spectrum with Raman spectroscopy observes the soft mode in the low-symmetry orthorhombic phase with the frequency softening as the pressure rises. Pressures above 9 GPa considerably transform the Raman spectra, indicating a structural phase transition.     

Harmonic analysis of coefficients of free energy decomposition in the polarization of a Rb<Subscript>2</Subscript>ZnCl<Subscript>4</Subscript> crystal

Landau–Devonshire decomposition coefficients W_C in a series with respect to P_C are determined via harmonic analysis of experimental free energy coordinates W_C of a Rb₂ZnCl₄ crystal, depending on its polarization P_C. The number of terms needed in W_C decomposition is determined for quantitative evaluation of the measured data.     

Lattice dynamics of BiFeO<Subscript>3</Subscript> under hydrostatic pressure

The vibrational frequencies of the BiFeO₃ crystal lattice in the cubic phase (Pm3m) and the rhombohedral paraelectric phase (R3c) are calculated in terms of the ab initio model of an ionic crystal with the inclusion of the dipole and quadrupole polarizabilities. In the ferroelectric phase with the symmetry R3c, the calculated spontaneous polarization of 136 μC cm^?2 agrees well with the experimental data. The dependences of the unit cell volume, the elastic modulus, and the vibrational frequencies on the pressure are calculated. It is found that the frequency of an unstable ferroelectric mode in both the cubic (Pm3m) and rhombohedral (R3c) phases are almost independent of the applied pressure, in contrast to classical ferroelectrics with a perovskite structure, where the ferroelectric instability is very sensitive to a variation in the pressure.