Study of structural phase transitions in (NH4)2SnBr6 by Raman scattering

The two successive phase transitions in (NH₄)₂SnBr₆ were examined by low- frequency Raman scattering experiments. Two low frequency modes which were assigned to the rotary modes of SnBr^2?₆ ions showed soft-mode like behavior in the lowest temperature phase. It was proposed that the higher phase transition is structural in nature associated with the soft rotary mode of the anions whereas the lower one is of an order-disorder type with respect to the relative orientations of the ammonium ions.     

Absorption spectra of C6H6 and C6D6 near 340 nm

The absorption spectra of C₆H₆ and C₆D₆ in the liquid phase have been studied near 340 nm. The absorption spectrophotometric mounting was a sequential double-beam attachment with linear response to energy on scanning of the spectrum before the exit slit and an electronic device which gives directly either the absorbance or the integrated absorbance of a transition and, consequently, its oscillator strength.The oscillator strength measured for the band of C₆H₆ is 8×10^?8, which corresponds to a dipole moment of 2.4×10^?3 Debye; this value is of the same order as a theoretical value calculated by Tsubomura and Mulliken (3.8×10^?3 Debye) for a transition between states ³F and ³A of an oxygen-benzene pair. This agreement corroborates the hypothetical existence of such a transition.The first vibrational band is at 28553 cm^?1 for C₆H₆; this band is not observed in the vapor or solid phase. It corresponds probably to the transition 0-0, which is considered in the literature to be near 29500 cm^?1. The isotopic shift measured for this first band is 164 cm^?1. The vibrational frequencies are, respectively, 910 cm^?1 for C₆H₆ and 889 cm^?1 for C₆D₆.     

Electron spin resonance investigation of the structural phase transitions in Alurea6(ClO4)3 and Ga urea6(ClO4)3

Second order structural phase transitions in Alur₆(ClO₄)₃ and Gaur₆(ClO₄)₃ with T_c ～ 300 K are studied by means of ESR on single crystals doped with the analogous Cr(III) compound. The transitions are antiferrodistortive and of the displacive type, the displacements resulting from the condensation of a X₂ mode $\text{(k = (0}\text{1}\text{2}\text{1}\text{2}\text{))}$ of the ClO₄ ions. The ESR parameters have the same temperature dependence as the order parameters and can be described by D and E～φ～. The space group describing the structure changes from S₆² to S₂¹, and the number of domains is multiplied by three. Above 300 K the crystals already consist of two domains, resulting from a ferrodistortive phase transition D_3d⁶ → S₆². The actual transition temperature of the latter phase transition lies at some temperature above the decomposition temperature of the crystals.     

Photoluminescence investigations on the nanoscale phase transition in Pb(Mg1/3Nb2/3)O3

The temperature dependence of the photoluminescence spectra of the relaxor ferroelectric Pb(Mg_1/3Nb_2/3)O₃ has been reported. The temperature behaviours of the 1.57, 1.67 and 1.73 eV bands indicate a phase transition at 110 K. This is attributed to a structural phase transition in the charged nanoshell. Analysis of the temperature dependence of 1.67 eV band intensity with a thermal quenching model indicated the existence of a phonon mode at 1153 cm⁻¹. This mode is identified in the Raman spectra measurement. The intensity of the 1.73 eV band showing an anomalous behaviour at 210 K is attributed to a transition from a crystalline phase to an amorphous phase in the charged nanoshell.     

A comment on the phase transition in RbCaF3

The structural phase transition in RbCaF₃ has been examined by observing super lattice points by means of neutron diffraction. There is one structural phase transition with the R₂₅^x soft mode phonon condensation up to 4.2 K. The rotation angle of CaF₆ octahedra, Ø, is calculated as 8.64 degrees at 60 K. The temperature dependence of Ø is also given.     

23Na nuclear magnetic resonance study of the phase transition in ammonium rochelle salt,NaNH4C4H4O6 • 4H2O

The satellite NMR spectrum of ²³Na in ammonium Rochelle salt (NaNH₄C₄H₄O₆ ? 4H₂O) is investigated near the transition temperature. Each line in the paraelectric phase splits discontinuously into four lines at the transition temperature; this fact is compatible with the first-order phase transition and reveals the existence of the superstructure in the ferroelectric phase.     

Phase transition of [(C6H5)3PCH3]+(TCNQ)-2 and electrical transport properties

The electrical conductivity at 10GHz, the dielectric constant, and the thermoelectric power (TEP) of [(C₆H₅)₃PCH₃]⁺(TCNQ)^-₂, from 230 up to 400 K, have been measured. This organic quasi-one-dimensional solid undergoes a first order phase transition at 314 K. At the transition the conductivity increases by a factor of 2.2 and the activation energy drops to 0.26 from 0.31 eV. At 314 K TEP decreases abruptly from -75 to -60μVK^-1 and remains almost constant for T > 314 K. The dielectric permeability ?₀ is constant and equal to 5 in the low temperature phase, increases abruptly by 7% at the transition, and then depends strongly on temperature in the high temperature phase. Results of the high temperature phase are interpreted in terms of a strongly correlated salt.     

Temperature and composition dependence of vibrational modes in Sm1−xLaxAlO3

At room temperature and for x₀ ～ 0.43, the system Sm_1?xLa_xAlO₃ undergoes a first order phase transition in which an orthorhombic structure transforms into a rhomboedral structure as x increases. This phase transition was investigated by Raman scattering experiments on polycrystalline compounds in the range 0 ? x ? 1. The dependence of low frequency modes on x is reported and compared with their well known temperature dependence. Soft modes have been observed in the orthorhombic (D_2h¹⁶) and rhomboedral (D_3d⁶) phases. It was found that the first order phase transition is probably driven by a double degenerate mode whose two components in the low symmetry phase display a linear composition dependence of their squared frequencies. The source of anomalous behaviour of Raman bands near the phase transition is discussed.     

Symmetry and lattice-dynamic aspects of structural phase transitions in (CH3NH3)2MnCL4 and related compounds

A group theoretical analysis of the second-order structural phase transition in (CH₃NH₃)₂MnCL₄ at 394°K and of similar transitions in ethyl and propyl compounds (D¹⁷_4h→D¹⁸_2h) was performed. The soft mode transforms according to the τ^x₅-irreducible representation at the X-point of the Brillouin-zone boundary and its eigenvector is discussed. The transition is of the order-disorder type and is caused by a slowing down of the hindered rotation of NH₃-groups. Knowing the symmetry of the order parameter, a thermodynamic potential expansion was constructed and expected anomalies in material constants around the transition temperature are briefly discussed. The high temperature phase transitions in analogous copper compounds are explained as a sequence D¹⁷_4h→D¹⁸_2h→D¹⁵_2h. The second of these phase transitions is driven by a soft mode transforming as the τ^Y₇-representation at the D¹⁸_2h Brillouin zone boundary.     

New phase transition in LiKSO4

A subtle first order phase transition in LiKSO₄ has been discovered with the help of a temperature dependent study of the Raman intensity measurements of certain polar modes in different polarization configurations. The room temperature hexagonal C⁶₆ (P6₃) phase transforms to trigonal C⁴_3v (P31c) phase at 201°K while cooling; the reverse transformation (on heating) takes place at 242°K. The phase transition appears to be primarily associated with a cooperative reorientation of SO₄ tetrahedra in the crystal.     

Electron hopping and optic phonons in Eu3S4

Raman scattering on single crystals of Eu₃S₄ does not show the allowed q=o phonon modes in the cubic phase and exhibits no new modes in the distorted low temperature phase (T<186 K). Above the Curie temperature T_c=3.8 K the scattering is dominated by a spin-disorder induced one-phonon density of states allowing for the observation of the zone boundary phonon breathing mode of the S^2?ions. This mode does not show any anomaly near the charge order -disorder phase transition T_t=186 K. Temperature tunable spin fluctuations associated with the temperature activated Eu²⁺→Eu³⁺ electron hopping are detected in the scattering intensity, superimposed on the usual thermal spin disorder.     

Raman scattering in K2Pt(CN)4Br0.3 · 3H2O

Raman scattering experiments on K₂Pt(CN)₄Br_0.3 · 3H₂O are reported between 5 and 300 K as a function of temperature. A line of A₁ symmetry detected at 44 cm^?1 shows interesting temperature dependent properties. It is concluded from a comparison of the frequency, symmetry, and scattering intensity of this line with theoretical predictions that the excitation concerned represents the amplitude mode of the charge density wave (the line observed in infrared absorption being the phase mode). No Peierls transition is observed, but the results are consistent with a Peierls distortion present at all temperatures. The findings are correlated with inelastic neutron scattering and infrared studies. Finally, the CN stretching modes at 2189 and 2173 cm^?1 and the water mode at 3490 cm^?1 are studied as a function of temperature.     

PHASE DEPENDENCE OF LUMINESCENT EMISSION OF Eu2+ DOPED SrAl2O4

In this work, we made five samples of SrAl₂O₄: Eu²⁺, Dy³⁺, the α phase and β phase SrAl₂O₄:Eu²⁺,Dy³⁺ powder and pellet samples, and α phase single crystal. We have measured the emission spectra of all the samples. All the emission peaks are around 520 nm, which correspond to the transition from 4f⁶5d¹(²E_g) to 4f⁷(⁸S_7/2) of Eu²⁺ in SrAl₂O₄ host. The intensity of emission of the β phase is stronger than that of the α phase. We believe that it is because the Eu²⁺ ions have occupied the two types of sites in the α phase SrAl₂O₄ host and the lifetime of the transition of Eu²⁺ in the A site is longer than that in the B site. This result also proves that the β phase of the material is brighter than the α phase. In addition, the β phase can be achieved by quenching technique.     

Synthesis and luminescent properties of Y6W2O15:Eu phosphors

In this paper, a novel phosphor, Y₆W₂O₁₅:Eu³⁺ was synthesized by thermal decomposition and phase transition of its decatungstate gel precursor. With stepwise increase of temperature to 750 °C, a crystalline phase of Y₆W₂O₁₅:Eu³⁺forms that gives intense red emission when excited at 466 nm, the emission is attributed to the Eu³⁺ ions transitions from ⁵D₀ excited states to ⁷F_J (J=0-4) ground states. The long excitation wavelength proves the Eu³⁺ transition follows the photoexcitation of the oxygen-metal (O→W lmct) charge transfer bands in yttrium tungstate. Some structural information regarding Y₆W₂O₁₅ provided by luminescence is in accord with that characterized by X-ray diffraction (XRD) and scanning electron microscope (SEM). The long-wavelength excitation properties of this material may find application in the production of red phosphors for white light-emitting diodes (LEDs).     

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.     

Raman spectrum of α and β-Pb3(PO4)2

The Raman spectrum of Pb₃(PO₄)₂ exhibits a progressive modification from the α to the β phase spectrum. No discontinuities are observed at the transition point.One soft mode of A_g type due to a translation mode parallel to the binary axis appears in the α phase.A strong broadening of the Rayleigh line is also observed above and below the transition point.     

Quasi two-dimensional electronic properties of the lithium molybdenum bronze,Li0.9Mo6O17

Four probe electrical resistivity measurements between 0.3K and 300K were made on single crystals of the violet-red bronze Li_0.9Mo₆O₁₇ grown by a temperature gradient flux technique. The temperature variation of the resistivity shows metallic conductivity and highly anisotropic behavior similar to K_0.9Mo₆O₁₇. The room temperature resistivity, measured in the direction parallel to the plate axis, is 9.5×10^-3Ωcm and 2.47Ωcm perpendicular to that axis. A phase transition observed at ～24K is possibly related to the onset of a charge density wave. A transition to the superconducting state is observed at Tc ～ 1.9K.     

Crystal structure and structural transition caused by charge-transfer phase transition for iron mixed-valence complex (n-C3H7)4N[FeFe(dto)3] (dto=C2O2S2)

(n-C₃H₇)₄N[Fe^IIFe^III(dto)₃] shows a new type of first order phase transition called charge-transfer phase transition around 120 K, where the charge transfer between Fe^II and Fe^III occurs reversibly. Recently, we have succeeded in obtaining single crystals of the title complex and determined the crystal structure at room temperature. Crystal data: space group P6₃, Z=2. Moreover, we have investigated the structural transition caused by the charge-transfer phase transition by means of powder X-ray diffraction measurement. When the temperature is decreased, the a-axis, which corresponds to the hexagonal ring size in two-dimensional honeycomb network structure of [Fe^IIFe^III(dto)₃]_∞, contracts by 0.1 Å at the charge-transfer transition temperature (T_CT), while the c-axis, perpendicular to the honeycomb network layer, elongates by 0.1 Å at T_CT. Consequently, when the temperature is decreased, the unit cell volume decreases without noticeable anomaly around T_CT, which is responsible for the quite small vibrational contribution to the entropy change, compared with usual spin crossover transition. Thus, the charge-transfer phase transition around 120 K for (n-C₃H₇)₄N[Fe^IIFe^III(dto)₃] is regarded as spin entropy driven phase transition.     

Mn2+ paramagnetic resonance and structural phase transitions in Rb2CdCl4

Structural phase transition in Rb₂CdCl₄: Mn²⁺ single crystal has been found near 133 K by EPR, X-ray and optical methods. Octahedral tilt system in the low temperature phase corresponds to the symmetry change D¹⁷_4h → D¹⁸_2h or D¹⁷_4h → C⁶_2h.     

Structures and phase transition in Rb2NaHoF6

The phase transition at T_c=172(2) K and high as well as the low temperature structures at 205 K and 17 K were studied with a low temperature Guinier diffractometer and camera. A second order phase transition (Γ-condensation of the T_1g mode) lowers the symmetry from Fm3m at T>;T_c to I4/m at T<T_c. In the low temperature phase the octahedra are tilted (5.2 degrees at 17 K) and slightly stretched. The increase of the tilt angle and the linear increase of the tetragonal distortion suggests a mean field power law. This classical behaviour would agree with the assumption of a Jahn Teller splitting of the Ho³⁺ electronic state.