Pressure dependence of the impurity soft modes in Li and Na : KTaO3

Low energy Raman scattering measurements on samples of K_0.76Na_0.24TaO₃, K_0.9Na_0.1TaO₃ and K_0.75Li_0.25TaO₃ under hydrostatic pressures of up to 60 kbar supply confirming evidence to the hypothesis that the Na⁺ ions in these crystals are displaced from the centers of the sites they occupy. The pressure Raman experiments also reveal another second order Raman line interpreted as Raman scattering by two TA phonons at M. A line induced by the substitution of Na for K is found to have an energy about equal to the energy of this new second order Raman line. It is shown that if this is a resonant mode it must be an even mode.     

Pressure dependence of the Raman spectra of indium sulphide

Raman spectra of InS single crystals have been studied at different hydrostatic pressures up to 1.2 GPa. Mode-Grüneisen parameters have been obtained for Raman-active normal modes. It is shown that the variations observed in Raman spectra with growing pressure can be interpreted from the standpoint of the structural phase transition D¹²_2h → D¹⁷_4h in InS as the hydrostatic pressure continues to increase. The transition pressure has been evaluated at (7 ± 1) GPa.     

The effects of incommensurability on the phonon modes in the one-dimensional superionic conductor K-hollandite

Polarized Raman and infrared spectra of the one dimensional (1-D) superionic conductor (K_2xMg_xTi(_8?x)O₁₆; x = 0.77) have been measured over the phonon frequency region 10–1000 cm^?1 as a function of temperature and pressure. The majority of the IR and Raman active modes predicted by group theory for the (Ti, Mg)O₆ framework were observed. The frequencies and their IR and Raman scattering cross-sections for the incommensurate lattice of K⁺ ions were calculated using a one dimensional linear chain model. This model assumes Coulomb interaction between nearest neighbors that are located in a sinusoidal potential due to the framework lattice. Several broad Raman bands were attributed to amplitudon type modes from the one dimensional incommensurate K⁺ ion sublattice. The IR active phason modes could not be identified unambiguously due to the underlying TiO framework vibrations which are known to possess large anharmonicity and oscillator strenghts.     

Raman scattering in brominated (SN)x crystals

Detailed Raman scattering data on brominated (SN)_x crystals ranging in composition from (SNBr_0.27)_x to (SNBr_0.55)_x, and preliminary Raman data on [SN(ICI)_0.125]_x are discussed. The investigation involved a study under various conditions of temperature, pressure and levels of bromination, of the two primary Raman lines at 154 and 230 cm^-1 in brominated (SN)_x, which are polarized along the polymer axis direction. The analysis of the data is consistent with a model in which bromine enters the interfibrillar regions as Br^-₃ and the (SN)_x lattice as Br₂. Infrared data is also presented showing an appreciable decrease in intensity of the SN modes at 995 and 670 cm^-1 on bromination.     

High-pressure Raman spectroscopy of antimony: As-type, incommensurate host-guest, and bcc phases

The vibrational dynamics of elemental solids that form incommensurate host-guest structures are of fundamental interest. High-pressure Raman scattering has been used to examine the vibrational spectrum of the group-V element Sb up to 33 GPa. A_1g and E_g phonons of the ambient pressure rhombohedral A7 phase display a marked decrease with pressure, i.e., prior to the transition to the tetragonal host-guest Sb-II phase at 8.6 GPa, via the monoclinic host-guest Sb-IV phase. The Raman spectrum of the incommensurate host-guest Sb-II phase, has five bands between 80 cm⁻¹ and 200 cm⁻¹ that increase with pressure. For the bcc structure stable above 28 GPa, we observe one weak disorder-induced band that increases with pressure.     

Raman scattering study of the dynamics of the pressure-induced phase transition in thallium azide (TlN3)

A Raman scattering investigation of the pressure-induced phase transition in tetragonal thallium azide (TlN₃) is reported. The most interesting features of the Raman spectrum of TlN₃ are the anti-resonant line-shapes of two E_g symmetry phonons at 35 and 50 cm^?1 superimposed on a quasi-elastic wing. The scattering data is shown to be consistent with a model in which the two phonons interact via an imaginary coupling term. The phonon at 35 cm^?1 (assigned to a translational shear mode of the Tl⁺ sublattice) softens with increasing pressure and increases in linewidth as P approaches P₀ (=8 kbar) from below. At the same time, the quasi-elastic scattering component (associated with large amplitude N₃^? librational fluctuations) becomes less damped. A displacive structural transition from tetragonal to monoclinic is indicated by the eigenvector of the soft phonon.     

The influence of hydrostatic pressure on Raman spectra of TIS and TlInSe2

First order Raman spectra of TIS and TlInSe₂ single crystals excited with 1.064μm line of the continuously operated YAG: Nd³⁺ laser have been investigated in equilibrium conditions under various hydrostatic pressures up to 1.08 × 10⁹ and 7.06 × 10⁸ Pa, respectively. Mode parameters γ_j = (1/ν_j)(dν_j/dP) were determined for all the Raman bands observed. Comparison of a set of these parameters in both crystals showed that the character of binding interatomic forces in these crystals appeared to be similar. For both crystals the intensity of Raman bands decreased with increasing the pressure.     

Spontaneous Raman scattering in atomic thallium vapor

Using a cw argon-ion laser, we have measured the spontaneous Raman scattering cross section, σ_R, and linewidth in atomic thallium vapor. For 4880-Å excitation, σ_R = 1.6 × 10^?27 cm². We observe no pressure broadening of the Raman line at vapor pressures to 100 torr.     

Raman scattering under pressure in ZnGa2Se4

The Raman scattering spectra of ZnGa₂Se₄ under pressure were investigated at 300 K up to 18.9 GPa. Two stages were observed in the pressure dependences of Raman bands. Such behavior in accordance with the experimental findings existing in literature and was attributed as arising due to the order–disorder phase transition in the cation sublattice.Using the Harrison–Keating's model of the lattice dynamics modified for the crystals with the tetragonal structure, the bulk modulus B and the mode-Grüneisen parameters Γ_i were determined for the first time. It is shown that a better agreement between the experimental and calculated values of Γ_i is observed, if one takes into consideration different frequency-pressure behavior for the bond-bending and the bond-stretching parameters, which determine the low- (lower than 140 cm⁻¹) and high- (higher than 140 cm⁻¹) frequency phonons, respectively.     

Resonant Raman scattering of polymeric sulfur nitride modified by iodine

Resonance Raman spectra of (SNI_y)_x crystals have been measured at 150 K. The energies of the principal Raman lines of the chromophore (109 and 154 cm^?1) and their intensity behaviour with exciting laser frequency are consistent with the formation of a charge-transfer complex in which iodine enters the interfiber regions of the (SN)_x lattice as I₅^- or I₃^- linked to distorted I₂ units. This structural model is supported by comparison of these Raman data with the excitation profiles of the chromophoric group in starch-iodine and α-cyclodextrine-iodine complexes. Possible mechanisms for the conductivity increase on the basis of the proposed charge transfer model are also discussed.     

A high pressure Raman study of TeO2 to 30 GPa and pressure-induced phase changes

The effect of pressure on the Raman modes in TeO₂ (paratellurite) has been investigated to 30GPa, using the diamond cell and argon as pressure medium. The pressure dependence of the Raman modes indicates four pressure-induced phase transitions near 1 GPa, 4.5 GPa, 11 GPa and 22 GPa. Of these the first is the well studied second-order transition fromD ₄ ⁴ symmetry toD ₂ ⁴ symmetry, driven by a soft acoustic shear mode instability. The remarkable similarity in the Raman spectra of phases I to IV suggest that only subtle changes in the structure are involved in these phase transitions. The totally different Raman spectral features of phase V indicate major structural changes at the 22GPa transition. It is suggested that this high pressure-phase is similar to PbCl₂-type, from high pressure crystal chemical considerations. The need for a high pressure X-ray diffraction study on TeO₂ is emphasized, to unravel the structure of the various high pressure phases in the system.     

Evolution of Raman and Mössbauer spectra at high pressures up to 75 GPa and a phase transition in CaSnO<Subscript>3</Subscript> perovskite

Raman and Mössbauer spectra from ¹¹⁹Sn nuclei in CaSnO₃ perovskite have been studied at high pressures up to 75 GPa. A linear increase in the frequency of the main Raman modes and a monotonic decrease in the isomer shift in Mössbauer spectra in the pressure range of 0–40 GPa are established. It is shown that the pressure-induced increase in Raman frequencies can be associated with the variation of the angle between the Sn–O–Sn bonds in chains of oxygen octahedra SnO₆ along the c axis. The sharp variation of the parameters of the Raman and Mössbauer spectra is observed in the pressure region of 40–55 GPa, indicating the structural phase transformations, which can be associated with the transition into the post-perovskite state. Raman spectra of CaSnO₃ samples with the ilmenite structure have been obtained for the first time.     

Pressure and temperature induced modification of luminescence from tetracene single crystals

Fluorescence spectra of crystalline tetracene have been recorded in the temperature range 120 to 300 K under hydrostatic pressure up to 600 MPa. From discontinuities in both emission spectra and spectral intensities it is concluded that two phase transitions occur. The room temperature phase is transformed to a low temperature phase/high pressure phase I at T^I_t (p = 0) = 182 K, the temperature coefficient being dT^I_t/dp = 0.395 K/MPa. The phase transition is induced by a decrease of the specific volume under pressure and/or upon cooling. Lack of a significant shift of the origin of the fluorescence band near T^I_t at constant pressure is an artifact resulting from the neglect of reabsorption effects. The Stokes shift is 260 cm^-1, independent of temperature and crystal modification. In accord with previous Raman data a second phase transition occurs at T^II_t (p) = 143 K, the pressure shift being dT^II_t/dp = 0.088 K/MPa.In addition, the shift of the triplet energy as a function of pressure as well as the pressure-dependence of the rate constants governing fission of a singlet exciton into a pair of triplets is discussed utilizing their magnetic field dependences.     

Photo-and pressure-induced transformations in the linear orthorhombic polymer of C<Subscript>60</Subscript>

Stability of the linear orthorhombic polymer of C₆₀ under pressure and laser irradiation is studied by Raman scattering and X-ray diffraction measurements. The Raman spectrum at ambient pressure remains unchanged, in the time scale of the experiment, up to an intensity of 3200 W/cm² of the 514.5 nm line of an Ar⁺ laser, but irreversible changes are observed at higher intensities. The Raman spectra recorded at increased pressure show similar irreversible changes even at the laser intensity as low as 470 W/cm². The X-ray diffraction and Raman measurements of the pressure-treated samples, performed after pressure release, show that the nonirradiated material does not exhibit any changes in the crystal structure and phonon spectra. This behavior indicates a pressure-enhanced photo-induced transformation to a new polymeric phase characterized by a Raman spectrum that differs from those of the other known polymeric phases of C₆₀. The Raman spectra of the phototransformed linear orthorhombic polymer of C₆₀ were measured at a pressure of up to 29 GPa. The pressure dependence of the Raman mode frequencies show singularities near 4 GPa and 15 GPa, respectively, related to a reversible phase transition and an irreversible transformation to a metastable disordered phase. The diffuse Raman spectrum of the disordered phase does not exhibit substantial changes with an increase in pressure up to 29 GPa. The high-pressure phase transforms to a mixture of pristine and dimerized C₆₀, after pressure release and exposure to ambient conditions for 30 h. The text was submitted by the authors in English.     

A Raman and NMR study of KSbF6

The ¹⁹F spin-lattice relaxation results in the laboratory frame show that upon cooling from the tetragonal phase, KSbF₆(I), the transition to the cubic phase, KSbF₆(II), occurs over a wide temperature range (~38 K) in which the two phases co-exist. The Raman results using powdered samples agree with this observation but co-existence of phases has of course not been observed in single crystal Raman measurements. Upon rapid cooling of the powdered samples in the Raman studies the tetragonal phase could be super-cooled. Upon heating from the cubic phase, the transition was observed at 302 ± 2 K in all the measurements. The Raman spectra of KSbF₆(I) give no evidence of a non-centrosymmetric structure but it is shown that this is so because the Sb-atoms are only very slightly displaced from centro-symmetrical positions. ¹⁹F second moment results are in agreement with a model in which the SbF^?₆-octahedra are stationary below 180 K and reorient isotropically above 260 K. The importance of scalar spin-spin coupling between fluorine and antimony nuclei is reflected by the T_1p results in the vicinity of the T₁ minimum. The Raman spectra of the cubic phase at higher and lower temperatures are different and the polarized spectra of single crystals are used to assign the bands in terms of a C₃-site group symmetry for the SbF^?₆-groups and a T unit cell group symmetry.     

Single crystal polarized Raman spectra of the solid electrolyte Cu2HgI4; attempt frequencies for ion motion in Ag2HgI4

The polarized Raman scattering from small single crystals of Cu₂HgI₄ provided assignments for the more prominent Raman features to specific irreducible representations. The E symmetry assignment, mass dependence, and pressure dependence of the 36 cm^?1 band in Cu₂HgI₄ and 24 cm^?1 band in Ag₂HgI₄ indicate that these features approximate the attempt frequency for ion hopping. The unusually high pre-exponential factor in the Arrhenius expression for ion hopping is discussed in light of the observed attempt frequency; we conclude that despite the high activation energy the conduction mechanism is similar to other heavy-metal solid electrolytes.     

Two-phonon Raman spectra of LiH and LiD crystals

The experimental two-phonon Raman spectra of LiD and LiH are reported here. A deformation dipole model formulated elsewhere for LiD is used to compute the lattice dynamics of LiD and LiH required in the Raman intensity calculations. The use of the same model for LiH is justified by the good agreement between the peak positions of the temperature-weighted two-phonon density of states and the various experimental spectra. The Raman intensity calculations are carried out by treating the second-order expansion coefficients in the polarisability tensor as adjustable parameters. The need for the parameters associated with the next-nearest-neighbor ions is clearly demonstrated for all the spectra. A single set of six parameters for the T₂₈ spectra and thirteen parameters for the E₈ (or A₁₈) spectra is found to explain all the experimental spectra of LiD and LiH quite well. Since the polarisability of Li⁺ is very small, the need for the second-neighbor positive-positive parameters reflects on the extended and highly polarisable nature of the H^? or D^? ion.     

Ionic liquids based on the bis(trifluoromethylsulfonyl)imide anion for high‐pressure Raman spectroscopy measurements

Assembling a diamond anvil cell for high‐pressure measurements involves placing in a gasket hole the sample of interest, a pressure transmitting fluid, and a material for pressure calibration. In this communication, we propose the use of ionic liquids containing the bis(trifluoromethylsulfonyl)imide anion ([Tf₂N]^‐), [(CF₃SO₂)₂ N]^‐, as a simultaneous pressure transmitting and calibrant material for high‐pressure Raman spectroscopy measurements of solid samples that are not soluble in ionic liquids. The position of the characteristic Raman band of the [Tf₂N]^‐ anion at 740 cm⁻¹ exhibits linear frequency shift for pressures up to 2.5 GPa. High‐pressure Raman spectra of different ionic liquids containing the same anion indicate that the actual magnitude of the pressure‐induced frequency shift of the [Tf₂N]^‐ normal mode depends on the counterion, the typical shift being 4.2 cm⁻¹/GPa. Ionic liquids based on the [Tf₂N]^‐ anion are also good pressure transmitting mediums because hydrostatic condition is kept at high pressure, and no crystallization is observed up to 4.0 GPa. Copyright © 2012 John Wiley & Sons, Ltd.     

Pressure and temperature dependence of Raman scattering and optical absorption in crystalline S4N4

Raman scattering and optical absorption in crystalline S₄N₄ have been measured both as a function of pressure at 295 K and low temperatures. Polarized single crystal Raman data were also obtained as an aid in the assignment of the Raman active phonons. The pressure coefficients of the Raman active external and S-S stretching modes show a discontinuity near 7 kbar indicative of a second order phase change. The optical absorption edge at about 2.5 eV of a sublimed film of S₄N₄ shows red shifts of 1.3 × 10^?5 eV bar^?1 and 6.3 × 10^?4 eV K^?1 with pressure and temperature respectively. In the light of these results, the electronic, vibrational and structural properties of the crystal are discussed.     

Raman spectra of TiO2-II,TiO2-III,SnO2, and GeO2 at high pressure

Raman spectra of the orthorhombic (II) and high pressure (III) phases of titanium dioxide at pressures to 372 kbar and effects of temperature and hydrostatic pressure on Raman spectra of the tetagonal cassiterite-like phases of TiO₂, GeO₂ and SnO₂ are described. At room temperature, the TiO₂ II–III transition is sluggish, and metastable coexistence was observed from 200 to 300 kbar. The Raman spectra of TiO₂-III imply that its primitive cell contains at least four formula units; however, the structure could not be established from the Raman spectra and available powder X-ray diffraction patterns.The temperature and pressure dependences of the spectrum of the tetragonal MO₂ phases together with bulk moduli and thermal expansion data were used to evaluate the pure-volume and pure-temperature contributions to the isobaric temperature dependence of the Raman frequencies. Large anharmonicities in TiO₂ are attributed to hybridization of the oxygen p states with the d states of the Ti ion. GeO₂, where p-electron bonding is involved, is much less Enharmonic.