Temperature‐induced phase transformations in Na2WO4 and Na2MoO4 crystals

Temperature‐dependent Raman studies on Na₂WO₄and Na₂MoO₄ crystals were performed in order to obtain information on structural changes induced by temperature evolution. The stability of the cubic phase of Na₂WO₄and Na₂MoO₄crystals was assessed and our results indicate that this phase is stable in the 8–823 K and 15–773 K ranges for Na₂WO₄ and Na₂MoO₄, respectively. The crystal of Na₂WO₄ shows a phase transition occurring at 833 K. Na₂MoO₄undergoes a sequence of three phase transitions, which were observed at 783–803, 823–913 and 943–950 K. In both crystals, a strong first‐order phase transition occurs as indicated by the behavior of the Raman modes: the Raman bands split and new bands appear below 100 cm⁻¹. These transitions are connected with tilting and/or rotations of the WO₄and MoO₄ tetrahedra, which leads to a disorder at the WO₄and MoO₄ sites. Copyright © 2010 John Wiley & Sons, Ltd.     

Temperature‐dependent Raman scattering studies of Na2MoO4

The mode assignment of the cubic phase of anhydrous Na₂MoO₄ was carried out on the basis of lattice dynamic calculation using the classical rigid‐ion model. Temperature‐dependent studies indicate that this crystal remains in the cubic structure in the 15–773 K range and undergoes a phase transition at around 783 K. The behavior of the Raman modes indicates that this transition is strongly first‐order in nature and the phase above 773 K may have an orthorhombic symmetry. This transition is connected with tilting and/or rotations of the MoO₄ tetrahedra, which lead to a disorder at the MoO₄ sites. Our results give also evidence that the Mo O bond lengths decrease in the high‐temperature phase. Copyright © 2008 John Wiley & Sons, Ltd.     

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.     

Raman scattering study of temperature and hydrostatic pressure phase transitions in Rb2KTiOF5 crystal

Raman spectra of Rb₂KTiOF₅ crystal were obtained and analyzed in the temperature range from 77 to 297 K and under hydrostatic pressure up to 4.2 GPa (at T = 295 K). The experimental results were compared with quantum‐chemical simulation of TiOF₅ pseudo‐octahedron. To interpret effects of lattice ordering, phonon spectra of several ordered phases of Rb₂KTiOF₅ were calculated within ab initio generalized Gordon–Kim model, and ordering of TiOF₅ molecular groups were simulated within Monte Carlo approach. The spectra exhibited orientation disordering in the cubic phase under ambient conditions. Cooling below the phase transition temperature (215 K) leads to partial ordering of the structure. The isotropic perovskite‐like phase was found to undergo first‐order transition into a low‐symmetry anisotropic phase at about 1 GPa. Further compression up to 4.1 GPa did not show any effects associated with phase transitions. Copyright © 2011 John Wiley & Sons, Ltd.     

Pressure-induced structural and electronic transition in KTb(MoO4)2 through Raman and optical studies

Raman and optical absorption studies under pressure have been conducted on KTb(MoO₄)₂ up to 35.5 GPa. A phase transformation occurs at 2.7 GPa when the crystal is pressurized at ambient temperature in a hydrostatic pressure medium. The sample changes to a deep yellow color at the transition and visibly contracts in theα-axis direction. The color shifts to red on further pressure increase. The Raman spectral features and the X-ray powder pattern change abruptly at the transition indicating a structural change. The pressure-induced transition appears to be a property of the layer-type alkali rare earth dimolybdates. However, the color change at the transition in KTb(MoO₄)₂ is rather unusual and is attributed to a valence change in Tb initiated by the structural transition and consequent intervalence charge transfer between Tb and Mo.In situ high pressure X-ray diffraction data suggest that phase II could be orthorhombic with a unit cell having 3 to 4% smaller volume than that of phase I.     

Phase transition in a NaBi(MoO<Subscript>4</Subscript>)<Subscript>2</Subscript> crystal: Acoustic investigations

This paper reports on the results of acoustic investigations of a NaBi(MoO₄)₂ crystal in the temperature range from 20 to 70°C. The temperature dependences of the velocity of longitudinal ultrasonic waves propagating along the crystallographic axes z and x are measured at a frequency of 4 MHz. The results obtained demonstrate that a structural phase transition occurs in the NaBi(MoO₄)₂ crystal at a temperature of 309 K. The experimental findings are consistent with the assumption that the observed phase transition is either a second-order ferroelastic transition or a first-order ferroelastic transition that is very close to being a second-order phase transition.     

Raman light scattering,infrared absorption and DSC studies of the phase transition and vibrational and reorientational dynamics of H2O ligands and ClO4– anions in [Ba(H2O)3](ClO4)2

[Ba(H₂O)₃](ClO₄)₂ between 90 and 300 K possesses two solid phases. One phase transition of the first‐order type at: = 211.3 K (on heating) and = 204.6 K (on cooling) was determined by differential scanning calorimetry. The entropy change value (ΔS ≈ 15 Jmol^–1 K^–1), associated with the observed phase transition, indicates a moderate degree of molecular dynamical disorder. Both, vibrational and reorientational motions of H₂O ligands and ClO₄^– anions, in the high‐temperature and low‐temperature phases, were investigated by Fourier transform far‐infrared and middle‐infrared and Raman light scattering spectroscopies. The temperature dependences of the full‐width at half‐maximum values of the bands associated with ρ_w(H₂O) mode, in both infrared (~570 cm^–1) and Raman light scattering (~535 cm^–1) spectra, suggest that the observed phase transition is not associated with a sudden change of a speed of the H₂O reorientational motions. Ligands reorient fast, with correlation time of the order of several picoseconds, with a mean activation energy value E_a = 5.1 kJ mol^–1 in both high and low temperature phases. On the other hand, measurements of temperature dependences of full‐width at half‐maximum values of the infrared band at ~460 cm^–1, associated with δ_d(OClO)E mode, and Raman band at ~1105 cm^–1, associated with ν_as(ClO)F₂ mode, revealed the existence of a fast ClO₄^– reorientation in phase I and in phase II, with the E_a(I) and E_a(II) values equal to 8.0 and 6.5 kJ mol^–1, respectively. These reorientational motions of ClO₄^– are slightly distorted at the T_C. Fourier transform far‐infrared and middle‐infrared spectra with decreasing of temperature indicated characteristic changes at the vicinity of PT at T_C, which suggested lowering of the crystal structure symmetry. All these experimental facts suggest that the discovered phase transition is associated with small change of H₂O ligands and somewhat major change of ClO₄^– anions reorientational dynamics, and with insignificant change of the crystal structure, too. Copyright © 2012 John Wiley & Sons, Ltd.     

Joint Raman spectroscopic and quantum chemical analysis of the vibrational features of Cs2RuO4

The Raman spectroscopic characterization of the orthorhombic phase of Cs₂RuO₄ was carried out by means of group theory and quantum chemical analysis. Multiple models based on ruthenate (VI+) tetrahedra were tested, and characterization of all the active Raman modes was achieved. A comparison of Raman spectra of Cs₂RuO₄, Cs₂MoO₄, and Cs₂WO₄ was also performed. Raman laser heating induced a phase transition from an ordered to a disordered structure. The temperature‐phase transition was calculated from the anti‐Stokes/Stokes ratio and compared with the ones measured at macroscopic scale. The phase transition is connected with tilting and/or rotations of RuO₄ tetrahedra, which lead to a disorder at the RuO₄ sites. © 2015 The Authors. Journal of Raman Spectroscopy published by John Wiley & Sons Ltd.     

Raman spectroscopy study of Na2MoO4·2H2O and Na2MoO4 under hydrostatic pressure

Raman spectroscopy measurements of polycrystalline Na₂MoO₄·2H₂O (NMHO) and Na₂MoO₄ (NM) under hydrostatic pressure (from 0 to 10 GPa) were performed. This study allowed us to monitor the stretching and bending vibrations of MoO₄ ions as well as the translational modes as a function of pressure. The pressure dependence of the wavenumbers of the modes indicates that the Na₂MoO₄·2H₂O undergoes two phase transitions at about ∼3 and ∼4 GPa. When releasing pressure, we have observed that the original spectrum is recovered, thereby pointing to a reversible process. The Na₂MoO₄ (NM) starting phase was found to be stable up to 10 GPa. The pressure‐dependent Raman data for NM did not reveal any structural modification. The influence of the pressure‐transmitting medium on the phase transitions is also discussed. Copyright © 2009 John Wiley & Sons, Ltd.     

Probing the ferroelectric phase transition in sol–gel‐derived polycrystalline bismuth ferrite thin films

Polycrystalline BiFeO₃ (BFO) thin films were successfully grown on Pt/Ti/SiO₂/Si(100) and SrTiO₃ (STO) (100) substrates using the chemical solution deposition (CSD) technique. X‐ray diffraction (XRD) patterns indicate the polycrystalline nature of the films with rhombohedrally distorted perovskite crystal structure. Differential thermal analysis (DTA) was performed on the sol–gel‐derived powder to countercheck the crystal structure, ferroelectric (FE) to paraelectric (PE) phase transition, and melting point of bismuth ferrite. We observed a significant exothermic peak at 840 °C in DTA graphs, which corresponds to an FE–PE phase transition. Raman spectroscopy studies were carried out on BFO thin films prepared on both the substrates over a wide range of temperature. The room‐temperature unpolarized Raman spectra of BFO thin films indicate the presence of 13 Raman active modes, of which five strong modes were in the low‐wavenumber region and eight weak Raman active modes above 250 cm⁻¹. We observed slight shifts in the lower wavenumbers towards lower values with increase in temperature. The temperature‐dependent Raman spectra indicate a complete disappearance of all Raman active modes at 840 °C corresponding to the FE–PE phase transitions. There is no evidence of soft mode phonons. Copyright © 2008 John Wiley & Sons, Ltd.     

蓝青铜K0.3MoO3单晶Peierls相变研究

测量了蓝青铜K_0.3MoO₃单晶Ｒ-Ｔ曲线，发现曲线在２８０Ｋ左右有异常变化，计算得到１８０Ｋ以下的半导体能隙为１３２０Ｋ（０.１１ｅＶ）．液氮温度下测量了晶体的非线性导电性，得到电场阈值为０.1２９Ｖ／ｃｍ．样品ＤＳＣ研究表明，样品在２４０Ｋ处经历一新的Ｐｅｉｅｒｌｓ相变，且为一级相变，据此对相变的微观性质进行了定量计算．１８０Ｋ附近Δｃ_p-Ｔ曲线表明，１８０Ｋ处的相变为一个二级相变加一个一级相变 关键词：     

Temperature‐dependent vibrational studies of [N(C2H5)4]2MnCl4

Room‐temperature polarized Raman spectra of a single crystal and IR spectra of a polycrystalline sample were measured for [N(C₂H₅)₄]₂MnCl₄ and the assignment of the observed bands to the respective modes has been proposed. Temperature‐dependent Raman and far‐IR studies were also performed for the polycrystalline sample in order to obtain information on changes occurring in this material as a result of phase transitions at T₁ = 227 K and at T₂ = 199 K. These studies revealed that the higher‐temperature ferroelastic phase transition is associated with significant modification of vibrational properties due to ordering of tetraethylammonium groups. The lower‐temperature phase transition does not lead to any clear changes in the spectra. However, our results suggest that disorder of MnCl₄²⁻ ions decreases with decreasing temperature. Copyright © 2007 John Wiley & Sons, Ltd.     

Structural transformations in a single‐crystal Rb2NaYF6: Raman scattering study

This paper reports Raman spectroscopy investigation of phase transitions in Rb₂NaYF₆ crystal. The experimental spectra were compared with the calculated one. The spectra were obtained in temperature range from 8 to 300 K. The Raman spectra shows anomalous temperature‐dependent behavior at T₁ = 154 and T₂ = 122 K. Soft mode restoration has been found, which allows us to attribute first transition at 154 K to displacive type. Detailed analysis temperature dependencies of the line positions and widths have been performed. We found no effects of possible lattice disorder anywhere, except narrow (about 20 K) range above the T₁ temperature. The Raman spectra of Rb₂NaYF₆ crystal have been obtained and analyzed under hydrostatic pressure up to 4.33 GPa (at T = 295 K). The high pressure experiment up to 4.33 GPa did not disclose any effects associated with phase transitions. The lattice vibration spectra were calculated up to 10 GPa. The calculation has been demonstrated that the Rb₂NaYF₆ does not undergo high pressure phase transition. Copyright © 2013 John Wiley & Sons, Ltd.     

Temperature‐dependent Raman spectroscopy study in MoO3 nanoribbons

This paper reports a study of vibrational, structural and morphological properties of molybdenum oxide nanoribbons. Temperature‐dependent Raman spectroscopy measurements in MoO₃ nanoribbons revealed morphological changes in the 150–350 °C temperature range. No structural phase transitions were observed, thus showing that the orthorhombic phase is stable from room temperature (nanoribbons) up to 650 °C (bulk‐like phase) where large plates have been formed by the coalescence of the nanoribbons. The interpretation of temperature‐dependent Raman data (wavenumber and linewidths) is supported by scanning electron microscopy that is used to directly probe the morphological changes in MoO₃ samples. The observed phenomena in the Raman data for MoO₃ nanoribbons can be applied to other nanomaterials. Copyright © 2012 John Wiley & Sons, Ltd.     

MREI‐model calculations of Raman‐active modes in layered mixed crystals TiS2−xSex(0≤x≤2)

A modified random‐element isodisplacement model has been developed and used to calculate the concentration dependence of the wavenumbers of Raman‐active modes in mixed crystal system, TiS_2−xSe_x(0≤x≤2). Earlier theoretical work, based on the Jaswal model, predicted a phase transition in this system on cooling up to 125 K temperature for the composition x ≥ 1.2. But recently reported resistivity measurements did not find the existence of any phase transition for a composition x < 1.4 on cooling. Our calculations show these findings and give remarkably better fitting to Raman data. The estimated values of the force constants are found to lie generally in the range 10⁵–10⁶ amu cm⁻². Copyright © 2007 John Wiley & Sons, Ltd.     

Synthesis and phonon properties of nanosized Aurivillius phase of Bi2MoO6

Nanosized crystallites Bi₂MoO₆ of a platelet shape were synthesized by a mild hydrothermal crystallization process. The effect of particle size on the structure and properties of Bi₂MoO₆ was studied by X‐ray diffraction, transmission electron microscopy, as well as Raman and infrared (IR) spectroscopies. Moreover, temperature‐dependent Raman spectra were collected for bulk and nanocrystalline Bi₂MoO₆. These studies showed that the thickness of the smallest crystallites is about 8–11 nm. Raman and IR studies have revealed that the damping and the intensity of Raman and IR bands are significantly modified with decreasing particle size and temperature. Moreover, some bands experience significant shifts both towards lower and higher wavenumbers. The obtained results indicate that, similar to the isostructural Bi₂WO₆, the orthorhombic distortion decreases with decreasing particle size. However, the structure of nanocrystalline Bi₂MoO₆ remains orthorhombic and noncentrosymmetric, and the structural changes are not the same as those observed in Bi₂WO₆. Copyright © 2010 John Wiley & Sons, Ltd.     

Temperature‐dependent Raman spectra of Ba2BiSbO6 ceramics

In this work, we have performed Raman scattering measurements in Ba₂BiSbO₆ ceramics in the temperature range from 10 to 573 K. The Raman spectra were examined using group theory to analyze the decomposition of the reducible representation of the vibrational modes and with a virtual octahedral model. At room temperature, five modes were observed. At low temperatures, the spectra subtly showed the rhombohedral–monoclinic phase transition, which was identified by changes in the Raman intensity of the bending and symmetrical stretching SbO₆ octahedral modes. The cubic–rhombohedral phase transition was not clearly evident in the high‐temperature Raman data. Copyright © 2009 John Wiley & Sons, Ltd.     

Raman analyses of co‐phasing and hysteresis behaviors in V2O3 thin film

We present the studies of the phase transition behaviors of V₂O₃ thin film using temperature‐dependent Raman scattering spectroscopy. Our results show that in both the cooling and heating processes of V₂O₃ thin film, the phase transition occurs gradually but not suddenly, contrary to that in single crystal. The coexistence of both the metal and insulator phases with co‐phasing ΔT_c larger than 30 K is observed in both the cooling and heating processes. We discuss that this large co‐phasing ΔT_c should be distinguished with the large hysteresis ΔT_h reported in nanostructures. In addition, our discussions indicate that co‐phasing ΔT_c and hysteresis ΔT_h would be mainly correlated with stress and defect states in sample, respectively. Furthermore, our Raman analyses suggest that stress would also induce phase transitions in V₂O₃, and the stress (pressure)‐induced phase transitions would behave differently comparing with the temperature‐induced transitions under normal pressure. Copyright © 2012 John Wiley & Sons, Ltd.     

Raman spectroscopic investigations on transition‐metal dichalcogenides MX2 (M = Mo,W; X = S,Se) at high pressures and low temperature

Transition‐metal dichalcogenides have been investigated using Raman spectroscopy both being off‐resonance and in resonance. The first‐order Raman spectra of MoS₂, MoSe₂, WS₂ and WSe₂ single crystal synthesized by vapor transport technique have been studied as a function of hydrostatic pressure (0–20 GPa) and temperature (80–300 K). Isobaric and isothermal mode‐Grüneisen parameters have been determined from the temperature and pressure‐dependent Raman spectra. The pressure dependence of the chalcogen–chalcogen and metal–chalcogen force constant has been obtained using a central force model. Separation of the temperature dependence of Raman mode wavenumbers into quasi‐harmonic and purely anharmonic contributions using measured high‐pressure Raman data allows us to extract the changes in the phonon wavenumbers arising exclusively due to anharmonic interactions. Copyright © 2014 John Wiley & Sons, Ltd.     

Structure and phase transitions in Cu2P2O7

X-ray diffraction studies of the temperature variation of the Cu₂P₂O₇ crystal structure were performed in the vicinity of the transition from the α-phase (C2/c space group) to the β-phase (C2/m space group). These results as well as those of Raman spectroscopy studies and temperature variation of the electric capacitance point to the existence of an intermediate phase in the temperature range 347–363?K.