Raman study of charge-density-wave phase transition in quasi-one-dimensional conductor (TaSe4)2I

Polarized Raman spectra were obtained in the quasi-one-dimensional conductor (TaSe₄)₂I above and below the charge-density-wave (CDW) transition temperature (T_c=263 K). The Raman intensities of many peaks become intenser and two of the phonon peaks shift to higher frequency with decreasing temperature. Moreover a new broad peak at about 90 cm^?1 and a new peak around 166 cm^?1 appear in the low-temperature phase. The polarization characteristic shows that the former is assigned to totally symmetric mode. The damping constant of the phonon at 90 cm^?1 increases markedly with increasing temperature. The frequency shifts to higher frequency as the temperature increases and the coupling coefficient is approximately proportional to (T_c?T)^{$\text{1}\text{2}$}. This peak becomes Raman active owing to the CDW phase transition. The temperature dependence of the damping constant and the frequency shift may have a relation to the dynamical properties of the CDW phase transition.     

Effect of temperature and pressure on the raman spectrum of As4S3

The Raman spectrum of crystalline As₄S₃ has been investigated as a function of temperature from 4 to 430 K at ambient pressure, and as a function of pressure to 70 kbar at ambient temperature. The external mode frequencies which appear clearly separated from the internal modes exhibit stronger pressure and temperature sensitivity compared to the latter modes. At the β-As₄S₃ to α-As₄S₃ phase transition near 410 K, the external modes change discontinuously indicating a first-order phase transition. The internal mode frequencies remain practically unaffected. The $\text{dv}\text{dP}$ and $\text{dv}\text{dT}$ data are analyzed using well established approaches. Application of non-hydrostatic pressure (>60 kbar) appears to destroy the crystallinity of As₄S₃.     

Electron diffraction and infrared study of the semimetallic layered compound Ti1−xVxSe2

The crystals of the system Ti_1?xV_xSe₂ (C ≤ x ≤ 0.05) undergo a second order structural phase transition. Electron diffraction studies show that the transition temperature decreases with progressive V-doping. The phase transition considerably affects the infrared reflectivity, measured at 300 and 77 K in the spectral range 40 cm^?1 to 4000 cm^?1.The presence of free carriers and the existence of optical infrared active E_u phonon modes $\text{(}\text{E}\text{⊥}\text{c}\text{)}$ confer their characteristic appearance to the spectra. At room temperature one phonon structure is measured at 143 cm^?1. At 77 K a new series of phonon peaks appears up to a V-concentration of 5 % as a direct consequence of superlattice formation.At room temperature the plasma-edge shifts towards higher frequencies as the vanadium concentration increases. This effect is caused by a large increase of $\text{N}\text{m}{}^1$, associated with the mixing of impurities. It is indicative of the small density of states at the Fermi level in semimetallic TiSe₂. Our results suggest a phase transition driven by lattice dynamical effects.     

Quantum melting of the charge-density-wave state in 1T-TiSe2

We report a Raman scattering study of low-temperature, pressure-induced melting of the charge-density-wave (CDW) phase of 1T-TiSe2. Our measurements reveal that the collapse of the CDW state occurs in three stages: (i) For P<5 kbar, the pressure dependence of the CDW amplitude mode energies and intensities are indicative of a "crystalline" CDW regime; (ii) for 525 kbar, the absence of amplitude modes reveals a metallic regime in which the CDW has melted.     

Neutron scattering study of the phase transition in s-triazine at high pressure

The elastic transition in s-triazine (C₃N₃H₃) from a trigonal ($\text{R}\text{3}\text{c}$) high temperature (low pressure) structure to a monoclinic (C2/c) low temperature (high pressure) phase has been investigated at pressures up to 5 kbar using neutron scattering techniques. Neutron diffraction was used to measure the pressure dependence of the order parameter and inelastic scattering to study the softening of the transverse acoustic phonon modes on three isotherms. In both cases the effect of pressure on the transition is found to be described primarily by that on the temperature of the transition.     

Successive Jahn-Teller transitions and the canted pseudospin state in K2PbCu(NO2)6

The successive phase transitions in K₂PbCu(NO₂)₆ has been studied by precise X-ray measurements. The unit cell in Phase III is doubled along each of the cubic principal axes. The experimental results can be interpreted as sequencial cooperative Jahn-Teller transitions where the higher transition is due to the coupling with the uniform distortion, while the lower transition is caused by the coupling with the uniform distortion, while the lower transition is caused by the coupling with the zone boundary phonon mode with $\text{k}{}_0\text{= (}\text{1}\text{2}\text{,}\text{1}\text{2}\text{,}\text{1}\text{2}$. The electronic state in Phase III is characterized as the “canted pseudospin” state.     

Hydrodynamics of an n-component phonon system

The dynamic properties of an n-component phonon system in d dimensions, which serves as a model for a structural phase transition of second order, are investigated. The symmetry group of the hamiltonian is the group of orthogonal transformations $\text{O}$(n). For n ≥ 2 a continuous symmetry is broken for T<T_c, where T_c is the transition temperature. We derive the hydrodynamic equations for the generators of this group, the $\text{1}\text{2}\text{n (n ? 1)}$ angular-momentum variables. Besides the usual hydrodynamics of a phonon system, there are $\text{1}\text{2}\text{n (n ? 1)}$ additional independent diffusive modes for T > T_c. In the ordered phase we find 2 (n ? 1) propagating modes with linear dispersion and quadratic damping. Formally the hydrodynamics is similar in the isotropic Heisenberg ferromagnet (n = 2) or the isotropic antiferromagnet (n ≥ 3). The relaxing modes for T < T_c require special care. We study the critical dynamics by means of the dynamical scaling hypothesis and by a mode-coupling calculation, both of which give the critical dynamical exponent $\text{z =}\text{1}\text{2}\text{d}$. The results are compared with the 1/n expansion. It is shown that for large n there is a non-asymptotic region characterized by an effective exponent $\text{z}\text{?}\text{= φ/2ν}$, where φ is the crossover exponent for a uniaxial perturbation, and ν the critical exponent of the correlation length.     

Soft phonon mode at the martensitic phase transformation of AuCuZn2

The lattice dynamical property of AuCuZn₂ has been investigated by means of inelastic neutron scattering technique in connection with its martensitic phase transformation. The temperature dependent soft phonon was observed transformation. The temperature dependent soft phonon was observed around $\text{q =}\text{2}\text{3}\text{[110]}$ of TA₂ phonon branch. We have also found a premartensitic metastable phase, in which new satellite reflections at (H± $\text{2}\text{3}$, K ? $\text{2}\text{3}$, 0) have been observed around fundamental reflections with H + K = 4n. The atomic displacements of the soft phonon mode correspond to the atomic arrangement of the premartensitic phase.     

A first principles lattice dynamics and Raman spectra of the ferroelastic rutile to CaCl2 phase transition in SnO2 at high pressure

A first principles calculation of the lattice dynamical properties of rutile SnO₂ has been performed using density functional perturbation theory at ambient and high‐pressure conditions to understand the pressure‐induced phase transition. The calculated zone centre phonon modes at ambient and high pressures have been compared with Raman scattering and infrared measurements. Full phonon dispersion curves and phonon densities of states and Raman intensities at high pressures are calculated and given for the first time in literature. The ferroelastic transition from the rutile to the CaCl₂‐type structure was confirmed. It is clearly illustrated that the first transition is associated with macroscopic shear instability which arises from the strong coupling between elastic constants and softening of Raman active B_1g mode. The observed pressure of phase transition in experimental measurements was reproduced more accurately than in previous calculations, and the difference between observed and calculated transition pressure is only of the order of 2%. The mode Grüneisen parameter is quantitatively as well as qualitatively different from the earlier reported values. Copyright © 2013 John Wiley & Sons, Ltd.     

Search for a sliding charge density wave in layered compounds

Non-linear voltage-current behavior is observed in the quasi one dimensional compound NbSe₃, due to the contribution of a sliding Charge Density Wave (CDW) to the conductivity. We have looked for a non-linear voltage-current characteristics in the incommensurate CDW state of the layered compounds 2H-TaSe₂ and 1T-TaS₂ and find no evidence for such up to $\text{1.0V}\text{cm}$ and $\text{10V}\text{cm}$, respectively. These values are several orders of magnitude higher than the minimum depinning field observed in NbSe₃.     

The vibrational spectra of magnesium pyrophosphate polymorphs

The Raman spectra were measured and analyzed for both α- and β-Mg₂P₂O₇. The IR and Raman spectra were interpreted for both phases using factor group analyses. The spectral features predicted with factor groups arising from the X-ray crystallographic space groups $\text{P2}{}_1\text{c}$ ? c⁵_2h and $\text{C2}\text{m}$ ? C³_2h for α-Mg₂P₂O₇ and β-Mg₂P₂O₇, respectively, fit the observed results. Bands observed in the Raman spectrum for β-Mg₂P₂O₇ are consistent with a linear bond angle while those for α-Mg₂P₂O₇ are consistent with a bent P-O-P bond angle. No soft modes were observed in the Raman spectra indicating that the phase transition between the two phases is not a second order process.     

Magnetic and elastic properties of CeAg

Magnetic and elastic measurements in single crystals of CeAg and Ce_0.09La_0.91 Ag are presented. The magnetic susceptibility of Ce_0.09La_0.91 Ag can be quantitatively interpreted with taking Γ₈ as the ground state of the crystal field split $\text{J =}\text{5}\text{2}$ state of the Ce³⁺-ion. In CeAg we confirm a ferromagnetic phase transition at T_c = 5.3 K and a structural transition at 15 K. This latter one is clearly observed with the elastic constant measurements where c₁₁ - c₁₂ exhibits appreciable softening. This structural transition is probably due to a phonon softening at the zone boundary. The magnetic properties of CeAg, especially the small magnetic moment in the ordered region, are discussed.     

Elastic constants of single crystals of the three phases of In---Pb alloys

In a study of the elastic behaviour of the InPb alloys, the elastic stiffness tensor components of crystals of each of the three phases (fct, $\text{c}\text{a}\text{> 1}$; fct, $\text{c}\text{a}\text{> 1}$; fcc) have been obtained as a function of temperature from pulse superposition measurements of ultrasonic wave velocities. Comparison of the elastic stiffness constants obtained for a fct ($\text{c}\text{a}\text{> 1}$) 5 atm.% Pb alloy with those of In itself and those of InTl and InCd alloys, establishes for this phase that alloying with Pb, as with TI and Cd, enhances the softening of the acoustic [110] phonon mode, polarization [1$\text{1}$0] near the Brillouin zone centre. The elastic properties of a 17 atm.% Pb crystal, which is in the fct ($\text{c}\text{a}\text{> 1}$) phase, are quite different from those shown by In alloys in the fct ($\text{c}\text{a}\text{> 1}$ phase; in particular the response to a shear stress is remarkably isotropie: there is no phonon mode softening in this alloy. Neither is there softening of this mode (which corresponds at the zone centre to the shear stiffness $\text{1}\text{2}$(C₁₁;C₁₂)) in crystals of the fee phase — in complete contrast to the dominating influence of the softening of $\text{1}\text{2}$(C₁₁;C₁₂) in the InTl and InCd fee alloys. In fact for a fcc In-75 atm.% Pb alloy the anistropy ratio for shear $\text{2C}{}_{44}\text{(C}{}_{11}\text{C}{}_{12}\text{)}$ is close to unity. The transitions between the three phases of the InPb alloys are markedly first order and acoustic mode softening has a much smaller influence on the elastic behaviour of the fct ($\text{c}\text{a}\text{< 1}$) and fcc InPb alloys than it has on the fct ($\text{c}\text{a}\text{< 1}$) InPb, InCd and InTl alloys.     

High temperature Raman scattering and phase transition in EuAlO3

Polarized Raman spectra of EuAlO₃ have been obtained at various temperatures from 77–1500 K. Three phonon modes are observed to soften in frequency with increasing temperature. Discontinuity in the frequency temperature dependence appears at 1420 K. This result is consistent with a first order phase transition. Analysis of the Raman data shows evidence of a coupling between the soft mode of Bg(XY) symmetry and one mode of same symmetry.     

Effect of two-photon saturation on ordinary Raman scattering

The excitation profile of ordinary Raman scattering under steady-state excitation conditions and the time-resolved emission spectrum of ordinary Raman scattering under transient excitation conditions undergo considerable changes when the excitation frequency ω approaches $\text{1}\text{2}$ ω_mn, where ω_mn is the resonance frequency of a two-photon transition from the ground state |n to an excited state |m of a molecule. The appearance of ghost peaks, dips or dispersion-like features centred at ω ? $\text{1}\text{2}$ ω_mn in the excitation profile and of coherence effects such as Rabi nutations with unusual time-dependence in the time-resolved spectrum are predicted.     

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.     

Raman scattering from electronic excitations of samarium in semiconducting and metallic Sm1−xYxS

The Raman spectra of Sm_1?xY_xS for $\text{x?0.4}$ have been measured. Electronic scattering between the J = 0 ground state and the J = 1 and 2 excited states of Sm²⁺ is observed. The singlet-triplet transition is observed on both sides of the black to gold phase transition in Sm_1?xY_xS.     

Raman study of phase transitions in rare earth vanadates

The phase transitions in DyVO₄ at about 14K and in TbVO₄ at about 33K have been investigated by Raman scattering. The E_g phonons are split below the transition temperature but the singlet phonon modes are not appreciably affected. No soft phonon mode is observed but large changes are seen in the low lying electronic levels. These results appear to be a consequence of a cooperative Jahn-Teller effect.     

Incommensurate superlattice reflections in quasi one dimensional conductors, (MSe4)2I (M=Ta and Nb)

X-ray diffraction and conductivity measurements have been made on (MSE₄)₂I, (M=Ta and Nb). A phase transition of (NbSe₄)₂I was found and the transition temperature T_c was determined to be about 210K by the conductivity measurement. For (TaSe₄)₂I, T_c was about 260K as reported previously. Superlattice reflections due to the formation of charge density wave (CDW) in (TaSe₄)₂I were observed at points $\text{q}\text{?}\text{=(±0.05, ±0.05, ±0.085)}$. The type of CDW of (NbSe₄)₂I is known to be identical to that of (TaSe₄)₂I. Temperature dependence of the threshold electric field of nonlinear conductivity is consistent with the result in previous reports.     

Resonance Raman spectroscopic study for radial vibrational modes in ultra‐thin walled TiO2 nanotubes

The study reports the observation of radial vibrational modes in ultra‐thin walled anatase TiO₂ nanotube powders grown by rapid breakdown anodization technique using resonant Raman spectroscopic study. The as‐grown tubes in the anatase phase are around 2–5 nm in wall thickness, 15–18 nm in diameter and few microns in length. The E_{g(ν1,ν5,ν6)} phonon modes with molecular vibrations in the radial direction are predominant in the resonance Raman spectroscopy using 325 nm He–Cd excitation. Multi‐phonons including overtones and combinational modes of E_{g(ν1,ν5,ν6)} are abundantly observed. Fröhlich interaction owing to electron–phonon coupling in the resonance Raman spectroscopy of ultra‐thin wall nanotubes is responsible for the observation of radial vibrational modes. Finite size with large surface energy in these nanotubes energetically favor only one mode, B_1g(ν4) with unidirectional molecular vibrations in the parallel configuration out of the three Raman modes with molecular vibration normal to the radial modes. Enhanced specific heat with increasing temperatures in these nanotubes as compared to that reported for nanoparticles of similar diameter may possibly be related to the presence of the prominent radial mode along with other energetic phonon mode. The findings elucidate the understanding of total energy landscape for TiO₂ nanotubes. Copyright © 2015 John Wiley & Sons, Ltd.