Lattice dynamics and Raman scattering spectrum of elpasolite Rb<Subscript>2</Subscript>KScF<Subscript>6</Subscript>: Comparative analysis

Raman scattering spectra of elpasolite Rb₂KScF₆ are studied in a wide temperature range including two phase transitions: from the cubic to the tetragonal phase and then to the monoclinic phase. The experimental Raman scattering spectrum is compared with the lattice vibration spectra of these phases calculated using an ab initio approach. A number of anomalies (caused by structural rearrangement during the phase transitions) are revealed and quantitatively analyzed in the ranges of both the intramolecular vibrations of the octahedron molecular ScF₆ ions and low-frequency intermolecular lattice vibrations. The interaction between low-frequency intramolecular vibrations and the intermolecular modes is found to be significant, and strong resonance interaction of the rotational soft modes (which are recovered below the phase transition points) with hard low-frequency vibrations of the rubidium ion sublattice is detected. These interactions are shown to substantially complicate the spectra.     

Structure and lattice dynamics of the high-pressure phase in the ScF3 crystal

The high-pressure phase of the ScF₃ crystal has been studied using synchrotron radiation diffraction and Raman scattering. This phase existing in the pressure range 0.6–3.2 GPa is optically anisotropic: its structure is described by space group R $ \bar 3 $ \bar 3 c, Z = 2, and the transition is associated with the rotation of ScF6 octahedra around the threefold axis. The pressure dependences of the lattice parameters and the rotation angle have been determined. The number of lines in the Raman spectrum corresponds to the expected number for this structure; the recovery of soft modes has been observed above the phase transition.     

Pressure-induced phase transition in the cubic ScF<Subscript>3</Subscript> crystal

Pressure-induced phase transitions in the ScF₃ crystal were studied using synchrotron radiation diffraction, polarization microscopy, and Raman spectroscopy. The phase existing in the range 0.6–3.0 GPa is optically anisotropic; its structure is described by space group R ₃ c (Z = 2), and the transition is due to rotation of ScF₆ octahedra around a threefold axis. The pressure dependence of the structural parameters and angle of rotation are determined. The number of Raman spectral lines corresponds to that expected for this structure; above the phase transition point, a recovery of soft modes takes place. At a pressure of 3.0 GPa, a transition occurs to a new phase, which remains metastable as the pressure decreases. The results are interpreted using an ab initio method based on the Gordon-Kim approach.     

EPR investigation of local paramagnetic centers in perovskite-like crystals

In ScF₃ single crystals (pure and doped) as well as in Rb₂KScF₆ and Rb₂KDyF₆ crystals with a perovskite-like structure, point nanodefects (vacancy in place of trivalent cations) have been found and studied. Electron paramagnetic resonance has been used to investigate local paramagnetic centers that are not detected using X-ray diffraction. The angular dependence of the spectra indicates a local distortion of the cubic symmetry of the crystals. An additional hyperfine structure in the observed spectra is due to the delocalization of electrons over six F^? ions forming the first coordination polyhedron around the vacancy. The crystals studied are characterized by a high electron mobility and a high electron velocity, which depends on the impurity. The high mobility of electrons of the cation center can be indirectly responsible for the structural phase transition occurring in the ScF₃ crystal under uniaxial pressure.     

A Raman scattering study of the phase transition in the (NH4)3WO3F3 oxyfluoride

The Raman scattering spectra of polycrystalline samples of the (NH₄)₃WO₃F₃ perovskite-like oxyfluoride were measured at frequencies of 70–3600 cm^?1 in the temperature range 93–323 K, including the transition from the orientationally disordered cubic phase to the low-symmetry phase. Transitional anomalies in the spectral parameters were revealed in the frequency ranges of internal vibrations of the ammonium ions and WO₃F₃ octahedral groups. An analysis of the experimental results allowed the conclusion that the phase transition under study is associated primarily with the ordering of the octahedral groups.     

Lattice dynamics and hydrostatic-pressure-induced phase transitions in ScF3

New phase transitions induced by hydrostatic pressure in a cubic (under standard conditions) ScF₃ crystal are discovered by the methods of polarization microscopy and Raman scattering. The space groups $R\bar 3c$ for Z=2 and Pnma for Z=4 are proposed for the high-pressure phases. A nonempirical computation of the lattice dynamics of the crystal is carried out. It is shown that, under normal pressure, the cubic phase is stable down to T=0 K, while the application of a hydrostatic pressure gives rise to a phonon branch in the vibrational spectrum (between points R and M of the Brillouin zone) with negative values of squares of frequencies. The condensation of soft mode R₅ at the boundary point of the Brillouin zone leads to rhombohedral distortion of the cubic structure with the unit cell volume doubling. The calculated frequencies at q=0 of the ScF₃ lattice in the distorted rhombohedral phase are real-valued; the number and position of frequencies active in Raman scattering are in accord with the experimental values.     

Raman spectroscopic study of the lattice dynamics in the Rb2KMoO3F3 oxyfluoride

The lattice dynamics of the Rb₂KMoO₃F₃ oxyfluoride has been studied by Raman spectroscopy in the temperature range 7–400 K. A phase transition has been revealed at T ≈ 185 K with decreasing temperature. Anomalies of the frequencies and Raman line half-widths have been analyzed. No condensation of soft lattice modes has been found. The character of changes in the Raman spectra of the Rb₂KMoO₃F₃ oxyfluoride shows that the phase transition is related to variations in the [MoO₃F₃]^3? molecular octahedron.     

Low‐temperature Raman spectra of racemate DL‐Alanine crystals

Raman spectra of DL ‐Alanine crystals were investigated in the 50–3200 cm⁻¹ spectral region for temperatures ranging from 15 to 295 K. The crystalline structure of DL ‐Alanine represents a rare example of an amino acid racemate crystallizing in a non‐centrosymmetric space group. From this study, we have observed changes in the wavenumber of modes associated with both rocking of CO₂⁻ and skeletal vibrations. On the other hand, neither changes in the modes associated to CH or CH₃ vibrations nor substantial modifications of the lattice modes of the crystal were observed. Such result indicates slight changes of the CO₂ group orientation without observation of a solid–solid phase transition in the DL ‐Alanine crystal. Copyright © 2009 John Wiley & Sons, Ltd.     

Lattice vibrational study of the phase transition in the plastic crystal adamantane (C10H16)

Using the Raman technique we have studied the lattice vibrations of the prototype plastic crystal adamantane (C₁₀H₁₆). The measurements, as a function of temperature through the phase transition (208K), show splittings in certain lines. At room temperature using hydrostatic pressure, we also induced a phase transition. The transition is detected by Raman measurements, and we observe splittings of the very same vibrational lines. This indicates that the pressure induced phase transition yields the same crystal structure as the low temperature structure. Some analysis of the pressure and temperature derivatives of the vibrational modes is presented.     

Double-electromagnetically induced transparency in a Y-type atomic system

We present secondary phase identification studies on Cr doped ZnO nanoparticles prepared by the sol-gel method. X-ray diffraction analysis confirms the formation of chromium oxides and there is found to be an increase of lattice parameter with thermal annealing. Scanning electron microscopic studies show the increase in the crystalline nature and particle size. Optical absorption measurements of the as prepared sample exhibit a strong band at 356 nm due to the free exciton absorption of the ZnO nanoparticles. An absorption band at 277 nm is due to the ³T₁ → ³T₂ transition in Cr⁴⁺ ions which appears only for the annealed samples. Photoluminescence studies show that deep level emission is completely suppressed after Cr₂O₃ formation/thermal annealing. Raman and FTIR spectra reveal formation of the Cr₂O₃ phase. Thermal annealing leads to the increase of crystalline nature which gives an enhancement to the Raman modes.     

Raman spectroscopy of the NH4MnCl3 crystal

The Raman spectra of the NH₄MnCl₃ crystal above and below the crystallographic phase transition are given for both the lattice and the ammonium modes. The results are discussed in terms of the structure of the crystal lattice and its influence on the symmetry of the ammonium ions.     

Lattice dynamics and the phase transition from the cubic phase to the tetragonal phase in the LaMnO<Subscript>3</Subscript> crystal within the polarizable-ion model

The paper reports on the results of ab initio calculations of the static and dynamic properties of the LaMnO₃ crystal with a perovskite structure in the cubic, rhombohedral, and orthorhombic phases. The calculations are performed within the ionic crystal model, which takes into account the deformability and polarizability of the ions. It is revealed that the spectrum of lattice vibrations in the cubic phase contains unstable vibrational modes, which occupy the phase space in the entire Brillouin zone. The eigenvectors of the softest mode at the boundary point R of the Brillouin zone are associated with the displacements of the oxygen ions and correspond to the “rotation” of the MnO₆ octahedron. The condensation of one, two, and three components of this mode leads to the tetragonal, orthorhombic, and rhombohedral distortions of the structure. The structural phase transition is described in terms of the local mode approximation with the use of the double perovskite unit cell, in which the MnO₆ octahedron is explicitly separated. The parameters of the model Hamiltonian are determined. The static properties are investigated by the Monte Carlo method. The calculated temperature of the phase transition from the cubic phase (9800 K) is considerably higher than the melting temperature of the crystal under investigation. The calculated frequencies of long-wavelength lattice vibrations in the experimentally observed orthorhombic and rhombohedral phases are in reasonable agreement with experimental data.     

Vibrational study of squaric acid

Infrared and Raman spectra of polycrystalline squaric acid and its deuterated derivative have been investigated at various temperatures in the 3600–30 cm^-1 range. Two infrared active lattice modes have been identified at 230 and 125 cm^?1 in the spectra at room temperature phase. A new assignment of some intramolecular vibrations involving OH and CO group is proposed. The behaviour of intramolecular and lattice bands as a function of temperature and phase transition is discussed.     

Raman scattering in Li2B4O7 crystals with impurities

Raman spectra of an Li₂B₄O₇ crystal containing potassium and silver impurity ions with a concentration in a range of 0.1–0.2% were studied in detail. In the scattering geometries corresponding to manifestation of totally symmetric polar vibrations, the redistribution of spectral intensity for some lines in a region of 450–570 cm^?1 was observed. Using the model of weakly interacting oscillators, parameters of vibrations in this region were determined. On the basis of present-day concepts of the theory of light scattering by impurities, the position of impurity ions in a crystal lattice is discussed.     

Raman spectroscopic study of the uranyl titanate mineral euxenite (Y,Ca,U,Ce,Th) (Nb,Ta,Ti)2O6

Raman spectra of the uranyl titanate mineral euxenite were analysed and related to the mineral structure. A comparison is made with the Raman spectra of uranyl oxyhydroxide hydrates. The observed bands are attributed to the Ti O and (UO₂)²⁺ stretching and bending vibrations, as well as lattice vibrations of rare‐earth ions. The Raman bands of euxenite are in harmony with those of the uranyl oxyhydroxides. The mineral euxenite is metamict as is evidenced by the intensity of the U O stretching and bending modes, which are of lower intensity than expected, and with bands that are significantly broader. Copyright © 2010 John Wiley & Sons, Ltd.     

Manifestation of a ferroelectric-antiferroelectric phase transition in Li<Subscript>0.12</Subscript>Na<Subscript>0.88</Subscript>Ta<Subscript>0.4</Subscript>Nb<Subscript>0.6</Subscript>O<Subscript>3</Subscript> in its Raman scattering spectra

The ferroelectric-antiferroelectric phase transition in the Li_0.12Na_0.88Ta_0.4Nb_0.6O₃ ceramic solid solution has been studied by the Raman scattering technique. As the temperature approached the transition point from below, we observed an appreciable broadening of the lines associated with the vibrations of the cations occupying octahedral and cubooctahedral cavities of the structure and with the oxygen network vibrations (which implies a substantial increase in disorder on the cation sublattices), as well as a decrease to zero intensity of the 875-cm^?1 line corresponding to stretch vibrations of the bridging oxygen in the BO₆ octahedral anion in the vicinity of the transition. The temperature dependence of the 875-cm_?1 line intensity near the transition was used to study the behavior of the phase transition order parameter η. The behavior of η was found to disagree markedly with the Landau theory of second-order phase transitions. It is shown that discrepancies originate from the increase in disorder in the niobium and tantalum sublattices in the Li_0.12Na_0.88Ta _y Nb_1-y O₃ solid solution system with increasing y. The order of the transition is lowered.     

Spectroscopic properties of alexandrite crystals II

Several aspects of the optical spectroscopic properties of alexandrite crystals not previously investigated are reported here. For Cr³⁺ ions occupying the Al³⁺ lattice sites with mirror symmetry in BeAl₂O₄, the positions of the zero-phonon lines for absorption transitions to the ²T_1g and ⁴T_2g levels are identified, and vibronic transition peaks in the fluorescence spectrum are compared to transitions appearing in the Raman spectrum and Stokes excitation spectrum. In addition, the effects of radiation trapping are shown to lengthen the fluorescence lifetime of the ²E_g - ⁴A_2g transition for ions in these sites at low temperatures. For Cr³⁺ ions occupying the Al³⁺ lattice with inversion symmetry, the ground state splitting of the ²E_g - ⁴A_2g transition is reported and the decrease of the fluorescence lifetime with temperature is shown to be due to the increase in vibronic emission probability as well as increased probability of direct radiationless decay.     

Study of the ion mobility in a Li0.03Na0.97Ta0.4Nb0.6O3 solid solution by raman spectra

We have studied ion mobility in a Li_0.03Na_0.97Ta_0.4Nb_0.6O₃ solid solution by its Raman spectra. It has been revealed that, as the temperature of the solution is increased to approach the point of the phase transition to a state with a high conductivity with respect to lithium, the lines with frequencies at 77, 118, and 142 cm^?1, which refer, respectively, to librations of oxygen octahedra Nb(Ta)O6 as a whole and vibrations of Li and Na ions in octahedra, considerably broaden, decrease in intensity, and smear into the wing of the Rayleigh line. Remaining lines are preserved in the spectrum. We have observed that the width of the line with a frequency of 118 cm^?1 depends exponentially on temperature, while the width of the line with a frequency of 142 cm^?1 changes linearly with it, which makes it possible to attribute to the line with the frequency of 118 cm^?1 to vibrations of Li⁺ cations, whereas the line with the frequency of 142 cm^?1 should be attributed to vibrations of Na⁺ cations in AO₁₂ cuboctahedra. The average lifetime of Li⁺ ions in equilibrium positions and the jump barrier have been estimated to be ～8 × 10^?12 s and ～20 kJ/mol, respectively. This agrees well with the data in the literature on measurements of electric conductivity.     

A raman scattering study of the phase transition in the ammonium oxyfluoride (NH4)3TiOF5

Raman spectra of a polycrystalline sample of the perovskite-like oxyfluoride (NH₄)₃TiOF₅ are measured in the frequency region 100–3600 cm^?1 at temperatures ranging from 91 to 370 K under hydrostatic pressures of up to 9 GPa, which include the range of the phase transition from the orientationally disordered cubic phase to the low-symmetry phase. Anomalies in the spectral parameters due to the phase transition are revealed in the range of vibrations of TiOF₅ octahedral groups.     

High-pressure Raman spectra of L-isoleucine crystals

Raman spectroscopy investigations of L-isoleucine crystals under high pressures have been carried out up to 7.3 GPa. From this study it was possible to observe modifications on bands associated to both rocking vibrations of r(NH₃⁺) and r(CO₂⁻) as well as to lattice modes at about 2.3 and 5.0 GPa. These modifications were correlated to either conformational change of molecules or to a solid–solid phase transition undergone by the crystals involving the hydrogen bonds that maintain the molecules held in the unit cell. A comparison with a few results on other amino acid crystals is also given.