Pressure-induced phase transitions for goethite investigated by Raman spectroscopy and electrical conductivity

We reported two pressure-induced phase transitions of goethite up to ～35?GPa using a diamond anvil cell in conjunction with ac impendence spectroscopy, Raman spectra at room temperature. The first pressure-induced phase transition at ～7.0?GPa is manifested in noticeable changes in six Raman-active modes, two obvious splitting phenomena for the modes and the variations in the slope of conductivity. The second phase transition at ～20?GPa was characterized by an obviously drop in electrical conductivity and the noticeable changes in the Raman-active modes. The variations in activation energy with increasing pressure were also discussed to reveal the electrical properties of goethite at high pressure.     

Pressure-induced phase transformation of CsPbI3 by X-ray diffraction and Raman spectroscopy

The structural transformation of cesium lead iodine (CsPbI₃) has been investigated in diamond anvil cells up to ～15 GPa at room temperature by employing synchrotron radiation X-ray diffraction and Raman spectroscopy. One reversible transformation from orthorhombic (Pnma) to monoclinic (P2₁/m) phase has been observed at 3.9 GPa. Isothermal pressure–volume relationship of orthorhombic CsPbI₃ is well fitted by the third-order Birch–Murnaghan equation of state with K₀ = 14(3) GPa, K′₀ = 6(2) and V₀ = 891(7) ų. The ultralow value of bulk modulus K₀ demonstrates the high compressible nature of CsPbI₃, similar to those of organic–inorganic metal halide perovskites. The present results provide essential information on the intrinsic properties and stability of CsPbI₃, which may be applied in photovoltaic devices.     

The application of Raman and anti-stokes Raman spectroscopy for in situ monitoring of structural changes in laser irradiated titanium dioxide materials

The use of Raman and anti-stokes Raman spectroscopy to investigate the effect of exposure to high power laser radiation on the crystalline phases of TiO₂ has been investigated. Measurement of the changes, over several time integrals, in the Raman and anti-stokes Raman of TiO₂ spectra with exposure to laser radiation is reported. Raman and anti-stokes Raman provide detail on both the structure and the kinetic process of changes in crystalline phases in the titania material. The effect of laser exposure resulted in the generation of increasing amounts of the rutile crystalline phase from the anatase crystalline phase during exposure. The Raman spectra displayed bands at 144 cm⁻¹ (A1g), 197 cm⁻¹ (Eg), 398 cm⁻¹ (B1g), 515 cm⁻¹ (A1g), and 640 cm⁻¹ (Eg) assigned to anatase which were replaced by bands at 143 cm⁻¹ (B1g), 235 cm⁻¹ (2 phonon process), 448 cm⁻¹ (Eg) and 612 cm⁻¹ (A1g) which were assigned to rutile. This indicated that laser irradiation of TiO₂ changes the crystalline phase from anatase to rutile. Raman and anti-stokes Raman are highly sensitive to the crystalline forms of TiO₂ and allow characterisation of the effect of laser irradiation upon TiO₂. This technique would also be applicable as an in situ method for monitoring changes during the laser irradiation process.     

高温高压下方解石相转变的拉曼光谱原位实验研究

用热液金刚石压腔装置结合拉曼光谱技术研究了高温高压下方解石的相变过程及拉曼光谱特征。结果表明:常温条件下,体系压力增至1 666和2 127 MPa时,方解石的拉曼特征峰155cm-1消失,1 087cm-1峰分裂为1 083和1 090cm-1两个谱峰、282cm-1峰突然降至231cm-1,证明其转变为方解石-Ⅱ和方解石-Ⅲ。在起始压力为2 761MPa和低于171℃的升温过程中,方解石-Ⅲ的拉曼散射的各个特征振动峰没有变化。当温度达到171℃,方解石晶体完全变成不透明状,其对称伸缩振动峰1 087cm-1、面内弯曲振动峰713cm-1和晶格振动峰155和282cm-1均发生突变,说明方解石-Ⅲ相变生成一种碳酸钙新相。体系降至常温,该新相一直保持稳定不变,表明高温高压下方解石向碳酸钙新相的转变过程是不可逆的。方解石-Ⅲ与碳酸钙新相之间的相变线方程为P(MPa)=9.09.T(℃)+1 880。碳酸钙新相的对称伸缩振动峰(ν1 087)随压力、温度的变化率分别为dν/dP=5.1(cm-1.GPa-1),dν/dT=-0.055 3(cm-1.℃-1)。     

Hard mode Raman spectroscopy and its application to ferroelastic and ferroelectric phase transitions

The application of Raman spectroscopy for the investigation of phase transitions focused traditionally on the observation of soft modes in displacive systems. The present furthergoing study on displacive and order-disorder systems is based on the observation of systematic changes of the scattering profiles of hard modes during the phase transition. It reveals the temperature evolution of the order parameters, the role of order-parameter fluctuations and phonon density of states effects in model systems like improper ferroelastic Pb₃(P_1-x As _x O₄)₂, lead diluted ferroelastic (Pb_1-x Ba _x )₃(PO₄)₂, pure ferroelastic As₂O₅ and the relaxor ferroelectric Pb(Sc_0.5Ta_0.5)O₃. Allied with supplementary experimental techniques hard-mode Raman spectroscopy (HMRS) is an ideal method for the investigation of order-parameter coupling effects and the characterization of structural phase transitions.     

A novel demonstration of photoacoustic Raman spectroscopy with combined stimulated Raman pumping in H2 molecule

We present the experimental demonstration of a novel, efficient, and vibrational selective technique to prepare population in vibrational level v″ = 1 using the stimulated Raman pumping. Photoacoustic Raman signal has been studied in non-radiative transitions in the molecule H₂ (v″ = 0) and (v″ = 1). The population fraction in the v″ = 1 level can be estimated by using combined photoacoustic Raman spectroscopy with stimulated Raman pumping for the first time.     

X-ray diffraction and Raman spectra of merrillite at high pressures

ABSTRACT

The compressibility and effect of pressure on the vibrations of merrillite, Ca₉NaMg(PO₄)₇, were studied by using diamond anvil cell at room temperature combined with in-situ synchrotron X-ray diffraction and Raman spectroscopy up to about 18 and 15?GPa, respectively. The pressure-volume data was fitted by a third-order Birch–Murnaghan equation of state to determine the isothermal bulk modulus as K₀ ?=?87.2(32) GPa with pressure derivative K₀′?=?3.2(4). If K₀′?=?4, the isothermal bulk modulus was obtained as 81.6(10) GPa. The axial compressibility was estimated and an axial elastic anisotropy exists since a-axis is less compressible than the c-axis. The Raman frequencies of all observed modes for merrillite continuously increase with pressure, and the pressure dependences of stretching modes (v ₃ and v ₁) are larger than those of the bending modes (v ₄ and v ₂) and external modes. The isothermal mode Grüneisen parameters and intrinsic anharmonicity of merrillite were also calculated.     

Temperature-induced phase transition in phlogopite revealed by Raman spectroscopy

Raman study of a natural hydrous phlogopite was carried out at temperatures up to 500 °C for the first time. Evolution of four well-resolved Raman modes at wavenumbers 196, 278, 322, and 682 cm⁻¹ was followed in detail with temperature increase. The analysis of data reveals linear decrease of vibrational wavenumbers in the studied temperature range, with small but experimentally significant discontinuities occurring at a temperature of 365±15 °C. Although the overall appearance of Raman spectra remains intact on crossing this temperature, the presence of discontinuities, as well as a marked difference between Gruneisen parameters calculated for high- and low-temperature ranges, signifies the presence of a temperature-induced phase transformation. By combining and correlating the results of the present Raman study with the high-temperature X-ray work performed by Tutti et al. [High-temperature study and thermal expansion of phlogopite, Phys. Chem. Miner. 27 (2000) 599-603] we arrive at the interpretation of a temperature-induced structural phase transformation in phlogopite without a significant symmetry change, with an underlying microscopic mechanism involving deformation of Mg octahedra and rotation of tetrahedral grid from ditrigonal toward hexagonal at the transition temperature.     

Probing structural stability of double-walled carbon nanotubes at high non-hydrostatic pressure by Raman spectroscopy

Theoretical calculations predict that the collapse pressure for double-walled carbon nanotubes (DWCNTs) is proportional to 1/R ³, where R is the effective or average radius of a DWCNT. In order to address the problem of CNT stability at high pressure and stress, we performed a resonance Raman study of DWCNTs dispersed in sodium cholate using 532 and 633 nm laser excitation. Raman spectra of the recovered samples show minor versus irreversible changes with increasing I _D/I _G ratio after exposure to high non-hydrostatic pressure of 23 and 35 GPa, respectively. The system exhibits nearly 70% pressure hysteresis in radial breathing vibrational mode signals recovery on pressure release which is twice that predicted by theory.     

In situ Raman spectroscopy of phase transformation in CrOx-Y2O3 system at elevated temperatures

A CrO_x-Y₂O₃ sample was prepared by a deposition-precipitation method and phase transformation of the sample under N₂ and air atmospheres was characterized by in situ Raman spectroscopy and X-ray diffraction (XRD) techniques. It was found that when the CrO_x-Y₂O₃ sample was heated, CrO₃ transformed to YCrO₄ and then to YCrO₃ and Cr₂O₃. Also, the transformation started from the surface region of the sample and then extended to the bulk, due to the fact that the phase transformation was detected by Raman spectroscopy at lower temperature compared to that by XRD. In addition, both atmosphere and temperature had influence on the phase transformation in the surface region, while the phase transformation in the bulk was merely dependent on the temperature. It was also found that low oxidation state Cr(III) species on the surface could be re-oxidized to high oxidation state Cr(V) or Cr(VI) species when the thermal treated sample was exposed to ambient air.     

高温高压下水溶液中硫酸根离子浓度的拉曼光谱定量测定研究

当前,拉曼光谱通常被应用于定性研究,拉曼光谱的定量研究明显不足。通过理论分析,拉曼光谱的定量研究应当基于其相对强度来进行。据此,通过对三种不同浓度的Na2SO4溶液进行拉曼光谱分析,得到了常温常压下水溶液中SO2-4离子浓度的定量方程为:c(SO2-4)=4.779 6R(r2=0.999 4)。此外,对高温高压下硫酸根水溶液的拉曼光谱也进行了研究。光谱分析表明,温度和压力将影响拉曼谱峰强度比值与SO2-4浓度的关系。高温高压下水溶液中SO2-4浓度的定量方程为:c(SO2-4)=4.779 6(R+1.469×10-4ΔT+1.340×10-4ΔP),式中c(SO2-4)为待测溶液中SO2-4的浓度,R为拉曼谱峰强度的比值R(SO2-4/H2O),ΔT为相对于常温(23℃)时的温度差,ΔP为相对于常压(0.1MPa)时的压力差。该方程适用的温度范围为23℃≤T≤360℃,浓度范围为0.5~1.5mol·L-1,测量的相对误差为6.5%。对于具有拉曼活性的物质,拉曼光谱实验技术可以用来进行水溶液中物质浓度的定量研究。     

High pressure behavior of nano-crystalline CeO2 up to 35 GPa: a Raman investigation

The present paper reports the results of in situ Raman studies carried out on nano-crystalline CeO₂ up to a pressure of 35 GPa at room temperature. The material was characterized at ambient conditions using X-ray diffraction and Raman spectroscopy and was found to have a cubic structure. We observed the Raman peak at ambient at 465 cm^?1, which is characteristic of the cubic structure of the material. The sample was pressurized using a diamond anvil cell using ruby fluorescence as the pressure monitor, and the phase evolution was tracked by Raman spectroscopy. With an increase in the applied pressure, the cubic band was seen to steadily shift to higher wavenumbers. However, we observed the appearance of a number of new peaks around a pressure of about 34.7 GPa. CeO₂ was found to undergo a phase transition to an orthorhombic α -PbCl₂-type structure at this pressure. With the release of the applied pressure, the observed peaks steadily shift to lower wavenumbers. On decompression, the high pressure phase existed down to a total release of pressure.     

Studies on Im-3-type KSbO3 using high pressure X-ray diffraction and Raman spectroscopy

In situ X-ray diffraction and Raman scattering experiments using a diamond anvil cell revealed that Im-3-type KSbO₃ remains stable up to 40.5?GPa with a bulk modulus K₀?=?101.6 (7)?GPa. Rietveld structure refinements and mode Grüneisen parameters suggested that the stability mechanism of this three-dimensional cubic tunnel structure was attributed to the isotropic compression for all types of Sb–O bonding in the unit of SbO₆ octahedron. Isotropic structure adjustment with external pressure reflected the nature that Im-3-type KSbO₃ model structure has a high ionic tolerance with a change in the chemical pressure in the isomorphous substitutions.     

Pressure-induced structural transitions in PbI2: A high-pressure Raman and optical absorption study

The effect of pressure on the 2H and 4H polytype of PbI₂ has been investigated by Raman and optical absorption spectroscopy, using the diamond anvil cell. The 2H-polytype undergoes pressure-induced phase transitions at 5 kbar and near 30 kbar. The 4H-polytype exhibits phase transitions near 8 kbar and above 30 kbar. The Raman modes abruptly change at these pressures. The optical absorption edge shifts red at the rate of 15±1 MeV/kbar in the 2H-PbI₂ and at the rate of 7 MeV/kbar in phase II. The latter phase is most likely to possess a 3d-structure and not a layer type. The possible structures for the high pressure phases are discussed.     

Phase Transition and vibration properties of MnCO3 at high pressure and high-temperature by Raman spectroscopy

The high pressure and high-temperature behavior of MnCO₃ was investigated up to 55?GPa at ambient temperature and up to 573?K at ambient pressure by Raman spectroscopy, respectively. Some new modes were detected at ～16 and ～32?GPa, which were assigned to MnCO₃-I below 16?GPa and to MnCO₃-II above 32?GPa, and to a coexisting phase of them in between. The high pressure vibration properties of all Raman modes, especially high frequency modes, were systematically reported. The coexisting phase of MnCO₃-I and MnCO₃-II had much easier compressibility than the MnCO₃-II phase. The thermal stability of MnCO₃ was at least to 573?K and its thermal expansion along the c axis was easier than a and b axes.     

Molecular dynamics in low vibrational states investigated by fs time-resolved coherent anti-Stokes Raman spectroscopy technique

The molecular dynamics process is investigated in this paper using a broadband fs time-resolved coherent anti-Stokes Raman spectroscopy (CARS) technique. By varying the timing of laser pulses, low vibrational states are started and studied on both the electronically excited B(³Π_0u⁺) state and ground X(¹Σ_0g⁺) state of iodine in the gas phase at room temperature. According to change the pump wavelength or Stokes pulse as well as the wavelength of the detection window for the CARS signal, dynamics on different potential-energy surfaces can be accessed and detected by the CARS spectroscopy. Results show that the period of the oscillation is decreased for the excited B(³Π_0u⁺) state as the wavelength of the pump pulses is increased, while it is increased for the ground X(¹Σ_0g⁺) state with the increase of the Stokes wavelength.