Charge density study under high pressure

The experimental and analytical method of the high-pressure powder experiment at BL10XU, SPring-8, is described. There is no doubt that BL10XU must be one of the most appropriate beam lines for high pressure X-ray diffraction experiment taking advantage of third generation synchrotron source. As an example of the advanced charge density study under high pressure, the structural change of Cs₂Au₂Br₆ by applying pressure is studied by Rietveld/MEM analysis. It reveals that the structural change of Cs₂Au₂Br₆ by applying pressure occurs basically at electron level, such as valence state change and chemical bonding, which may be called the electronic phase transition.     

First-principles calculations of structural stability and mechanical properties of tungsten carbide under high pressure

The structural stability and mechanical properties of WC in WC-, MoC- and NaCl-type structures under high pressure are investigated systematically by first-principles calculations. The calculated equilibrium lattice constants at zero pressure agree well with available experimental and theoretical results. The formation enthalpy indicates that the most stable WC is in WC-type, then MoC-type finally NaCl-type. By the elastic stability criteria, it is predicted that the three structures are all mechanically stable. The elastic constants C_ij, bulk modulus B, shear modulus G, Young?s modulus E and Poisson?s ratio ν of the three structures are studied in the pressure range from 0 to 100 GPa. Furthermore, by analyzing the B/G ratio, the brittle/ductile behavior under high pressure is assessed. Moreover, the elastic anisotropy of the three structures up to 100 GPa is also discussed in detail.     

The Raman spectroscopic studies of aligned MWCNTs treated under high pressure and high temperature

The study of the aligned multiwalled carbon nanotubes (MWCNTs) for interlinking bonding under high pressures and temperatures have been conducted in the diamond anvil cell. The MWCNT samples were analyzed using the Raman spectroscopy, when treated under the combinations of pressure and temperature ranges of 2-20 GPa and 25-500 °C. The analyses show the formation of interlinking bonding at a pressure above 2.5 GPa when treated under the temperature 500 °C, based on the significant change of the relative intensity between D- and G-bands in the Raman spectra. Comparisons of the data obtained before and after the high pressure and high temperature treatments are reported. The result indicates that the aligned MWCNTs may be easier to form the interlinking bonding compared to randomly oriented MWCNTs.     

Influence of vapor transport equilibration on Raman spectra of Er:LiNbO3 crystals

Raman spectra of as-grown and vapor transport equilibration (VTE) treated Er:LiNbO₃ crystals, which have different cut orientations (X-cut and Z-cut), different Er-doping levels (Er:(0.2, 0.4 and 2.0 mol%)LiNbO₃) and different VTE durations (80, 120, 150 and 180 h), were recorded at room temperature in the wavenumber range 50-1000 cm⁻¹ by using backward scattering geometry. The spectra were attributed on the basis of their spectral features and the previous experimental work and the most recent theoretical progress in lattice dynamics on pure LiNbO₃. In comparison with the pure crystal the most remarkable effect of Er-doping on the Raman spectrum is observed for the E(TO₉) mode. It does not appear at 610 cm⁻¹ as the pure crystal, but locates at 633 cm⁻¹. In addition, the doping also results in the lowering of the Raman phonon frequency, the broadening of the Raman linewidth and the changes of the relative Raman intensity of some peaks. The VTE treatment results in the narrowing of the linewidth, the recovery of the lowered phonon frequency and the further changes of relative Raman intensity. The narrowing of Raman linewidth indicates that the VTE processing has brought these crystals closer to stoichiometric composition. The VTE treatment has induced the formation of a precipitate ErNbO₄ in the high-doped Er(2.0%):LiNbO₃ crystals whether X- or Z-cut. For these precipitated crystals, besides above linewidth and phonon frequency features, they also display more significant Raman intensity changes compared with those not precipitated crystals. In addition, a slight mixing between A₁(TO) and E(TO) spectra is also observed for these precipitated crystals. Above doping and VTE effects on Raman spectra were quantitatively or qualitatively correlated with the characteristics of the crystal structure and phonon vibrational system.     

Phase transition of Ta2NiO6 with the trirutile-type structure under high pressure and high temperature

High-pressure phase transition of Ta₂NiO₆ with the trirutile-type structure was investigated from the viewpoint of crystal chemistry. A new quenchable high-pressure phase was found in the pressure range higher than 7 GPa and 900°C. The high-pressure phase has an orthorhombic cell (a=4.797(1) Å, b=5.153(2) Å and c=14.85(1) Å and space group; Abm2), and it is more dense by 9.6% than the trirutile-structured phase. Infrared spectra of the trirutile-type phase and the high-pressure phase show that Ni²⁺ ions in the high-pressure phase are still in octahedral sites. The crystal structure of the high-pressure phase is considered as a cation-ordering trifluorite-type structure, which can be stabilized by a crystal field effect of Ni²⁺ ions.     

A high-pressure Raman and X-ray diffraction study of the perovskite SrCeO3

A high-pressure structural study of SrCeO₃ has been performed at room temperature by Raman spectroscopy and X-ray diffraction up to 32 and 45 GPa, respectively. A first-order reversible phase transition is observed at about 12 GPa in both techniques. A second weak structural change, taking place between 18 and 25 GPa, can be suspected from Raman data. The increase in the number of Raman bands and diffraction lines is an indication that the symmetry is lowered and the compound does not evolve towards the ideal cubic perovskite structure. A Rietveld analysis of X-ray data was performed for the low-pressure phase and the atomic positions and the cell lattice parameters variations are reported in this paper. The volume compressibility derived from Raman modes (5.6×10⁻¹² Pa⁻¹), involving mainly bond-stretching for each type of polyhedron, is found to be close to the one obtained from volume cell variations measured by X-ray diffraction (7.9×10⁻¹² Pa⁻¹).     

Structure and high pressure behaviour of organic crystals based on aromatically substituted 1,3,4-oxadiazoles

The crystalline structure of a new compound containing the 1,3,4-oxadiazole moiety, 4-(5-methyl-1,3,4-oxadiazole-2yl-)-N,N′-dimethyl-phenylamine (MODPA) was determined. It shows a monoclinic structure with space group P2₁/c and lattice parameters: a=1.02997(6), b=0.64840(4), c=1.58117(10) nm and β=99.4820(10)°. To study the intermolecular interactions in oxadiazole containing organic crystals, X-ray studies on MODPA and 2,5-diphenyl-1,3,4-oxadiazole (DPO) were performed up to 5 GPa at room temperature. The Murnaghan equation of state is used to describe the compression behaviour of both substances. From these results, the bulk modulus and its pressure derivative were determined. The values obtained are: K₀=6.3 GPa and K′₀=6.8 for MODPA and K₀=7.3 GPa and K′₀=6.7 for DPO. Additionally, measurements under increasing temperature at ambient pressure were carried out to evaluate the thermal expansion coefficient: α=1.8×10⁻⁴ K⁻¹ for MODPA and α=1.9×10⁻⁴ K⁻¹ for DPO.     

Doping dependence of the electronic Raman spectra in cuprates

We report electronic Raman scattering measurements on Bi₂Sr₂(Y_1−xCa_x)Cu₂O_8+δ single crystals at different doping levels. The dependence of the spectra on doping and on incoming photon energy is analyzed for different polarization geometries, in the superconducting and in the normal state. We find the scaling behavior of the superconductivity pair-breaking peak with the carrier concentration to be very different in B_1g and B_2g geometries. Also, we do not find evidence of any significant variation in the lineshape of the spectra in the overdoped region in both symmetries, while we observe a reduction of the intensity in B_2g upon decreasing photon energies. The normal state data are analyzed in terms of the memory-function approach. The quasiparticle relaxation rates in the two symmetries display a dependence on energy and temperature which varies with the doping level.     

Theoretical studies on the high pressure phases of Lanthanum monochalcogenides

We report total energy and electronic structure calculations for lanthanum monochalcogenides in B1 (NaCl) and B2 (CsCl) crystal structures over a range of unit cell volumes. We employed the tight binding linear muffin-tin orbital approach to density functional theory within the local density approximation to expand the crystal orbitals and periodic electron density. In agreement with the experiment we find that B1 phase is lower in energy than B2 phase, and that the compounds transforms to B2 structure under applied pressure. This is the first qualitative prediction of the transition in La monochalcogenides and should be testable with diamond-anvil technique.     

Structural stability of tin clathrates under high pressure

High pressure Raman scattering experiments have been performed for Rb₈Sn₄₄□₂ in order to investigate the pressure induced phase transition. At pressures of 6.0 and 7.5 GPa, Raman spectrum was drastically changed, indicating the phase transitions. The irreversibility of the spectral change and the disappearance of Raman peak observed at 7.5 GPa strongly suggest the occurrence of irreversible amorphization.     

高温高压下草酸脱羧反应中的拉曼光谱研究

应用水热金刚石压腔结合拉曼光谱技术研究了高温高压下草酸溶液的热稳定,使用拉曼光谱对其脱羧反应及产物进行监测。结果表明低温升温过程中,草酸的拉曼谱图中各个特征振动峰没有发生变化,随着温度的继续升高,其特征振动峰逐渐变弱。达到一定温度后,羧基的拉曼特征峰消失,草酸发生脱羧反应:C2H2O4—2CO2+H2生成CO2和H2。高温高压下草酸发生热分解的温度压力之间呈线性关系,其线性回归方程为P(MPa)=12.839 T(K)-5 953.7,R2=0.99。草酸脱羧反应的摩尔体积变化与温度压力的关系为ΔV(cm-3.mol-1)=16.69-0.002P(MPa)+0.005 2T(K),R2=0.99。     

Sulfur-catalyzed phase transition in MoS2 under high pressure and temperature

We report phase transition and stability of MoS₂ with and without the presence of sulfur melt under high-pressure and high-temperature conditions. Rhombohedral (3R) phase is found to be a high-temperature phase of MoS₂ at high pressures. Excess sulfur melt catalyzes the hexagonal (2H) to rhombohedral (3R) phase transformation and lowers the conversion temperature by more than 280 K. Boundary between 2H and 3R phases has been delineated with a negative slope. Based on experimental observations, sulfur-catalyzed 2H→3R transformation mechanisms are proposed involving atomic exchange between MoS₂ and sulfur, which is different from the case of without excess sulfur that proceeds through rotation and translation of the S–Mo–S sandwich layers.     

Phase transitions in 1,3,4-oxadiazole crystals under high pressure

Crystalline 2,5-di(4-nitrophenyl)-1,3,4-oxadiazole (DNO) has been investigated at pressures up to 5 GPa using Raman and optical spectroscopy as well as energy dispersive X-ray techniques. At ambient pressure DNO shows an orthorhombic unit cell (a=0.5448 nm, b=1.2758 nm, c=1.9720 nm, density 1.513 g cm⁻³) with an appropriate space group Pbcn. From Raman spectroscopic investigations three phase transitions have been detected at 0.88, 1.28, and 2.2 GPa, respectively. These transitions have also been confirmed by absorption spectroscopy and X-ray measurements. Molecular modeling simulations have considerably contributed to the interpretation of the X-ray diffractograms. In general, the nearly flat structure of the oxadiazole molecule is preserved during the transitions. All subsequent structures are characterized by a stack-like arrangement of the DNO molecules. Only the mutual position of these molecular stacks changes due to the transformations so that this process may be described as a topotactical reaction. Phases II and III show a monoclinic symmetry with space group P2₁/c with cell parameters a=1.990 nm, b=0.500 nm, c=1.240 nm, β=91.7°, density 1.681 g cm⁻³ (phase II, determined at 1.1 GPa) and a=1.890 nm, b=0.510 nm, c=1.242 nm, β=89.0°, density 1.733 g cm⁻³ (phase III, determined at 2.0 GPa), respectively. The high-pressure phase IV stable at least up to 5 GPa shows again an orthorhombic structure with space group Pccn with corresponding cell parameters at 2.9 GPa: a=0.465 nm, b=1.920 nm, c=1.230 nm and density 1.857 g cm⁻³. For the first phase a blue pressure shift of the onset of absorption by about 0.032 eV GPa⁻¹ has been observed that may be explained by pressure influences on the electronic conjugation of the molecule. In the intermediate and high-pressure phases II–IV the onset of absorption shifts to increased wavelengths due to larger intermolecular interactions and enhanced excitation delocalization with decreasing intermolecular spacing.     

Raman spectra and structure of a 25mer HCV RNA

We have employed Raman spectroscopy to investigate the conformation of an (Hepatitis C virus) HCV RNA 25mer (1–25 nucleotides) in solution. The principal findings of this study are (1) the A‐form secondary structure involving C3′‐ endo/anti ribofuranose pucker is predominant; (2) some uridine and guanosine nucleoside residues adopt the C2′‐ endo/anti and C3′‐ endo/syn conformations, respectively, which appear in looped nucleotide sequences; and (3) six out of nine guanine residues are base‐paired probably forming a stem. These results are interpreted as formation of a hairpin whose secondary structure is consistent with that proposed on the basis of phylogenetic comparisons with other viral RNAs. Copyright © 2009 John Wiley & Sons, Ltd.     

Temperature dependent study of the crystal structure of NaCdZn2F7 pyrochlore

NaCdZn₂F₇ pyrochlore (Fd3¯m, Z=8), in which the Na and Cd cations are completely disordered, is shown to be structurally stable in the temperature range 100-643 K using X-ray diffraction and Raman scattering at atmospheric pressure. X-ray single-crystal measurements indicate that the (Na, Cd)F₈ cubes become more regular, while the ZnF₆ octahedra become more distorted in this structure upon cooling. The anomalous temperature-dependence of one of the Raman-active mode has been observed.     

Raman spectra of samarium-fullerene intercalation compounds

Samarium-fullerene intercalation compounds of nominal composition Sm_xC₆₀ (x=1,2,…,6) have been synthesized by a solid-state reaction method. We obtain a Sm_2.75C₆₀ superconducting phase with orthogonal structure and a Sm₆C₆₀ phase with body-centered cubic structure. The broadening and weakening of Raman peaks of the Sm_xC₆₀ compounds are due to the distortion of C₆₀ and electron-phonon interaction. The Raman measurements reveal that the distortion of C₆₀ decrease in Sm_xC₆₀ (x=3,4,5) exposed to air, although the fulleride solids have transformed into an amorphous state. The Raman results also show that the distortion of C₆₀ is still very large in the Sm₆C₆₀ exposed to air, or the C₆₀ molecules have been destroyed and become some amorphous carbide.     

Electrical property and phase transition of CdSe under high pressure

In situ electrical resistivity measurement of CdSe was performed under high pressure and moderate temperature using a diamond anvil cell equipped with a microcircuit. With the pressure increasing, a sharp drop in resistivity of over two orders of magnitude was observed at about 2.6 GPa, it was caused by the transition to the rock-salt CdSe. After that, the resistivity decreased linearly with pressure. However, in different pressure range, the decreasing degree was obviously different. This attributed to the different electron structures. By fitting to the curve of pressure dependence of resistivity in different pressure range, the relationship of the band gap to pressure was given and the metallization pressure was speculated to be in the range of 70-100 GPa. The temperature dependence of resistivity showed that in the experimental temperature and pressure range the resistivity had a positive temperature coefficient.