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。     

Effect of solvation on polarization characteristics of fluorescence for 1,3,4-oxadiazole derivatives in binary solvents

We have studied the degree of fluorescence polarization for 1,3,4-oxadiazole derivatives in the binary solvents hexane-ethanol, toluene-ethanol, toluene-acetonitrile, 2-propanol-water, dioxane-water, 2-propanol-glycerol, glycerol-water vs. the composition of the solvent. We have shown that in systems with predominant universal interactions, the characteristic changes in the degree of polarization reflect the change in the viscosity of the mixture, while in systems with pronounced specific interactions they reflect the characteristic structural features of the fluorescent centers. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 75, No. 5, pp. 677–683, September–October, 2008.     

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.     

Low temperature,high pressure Raman study of SbSBr

Abstract

We have measured the Raman spectra of the quasi-one-dimensional crystal SbSBr as a function of pressure at 295, 70, 37 and 25 K.

The pressure coefficients of the observed Raman modes have been determined and used to distinguish inter-from intrachain modes. Spectral features characteristic of the ferroelectric phase have been attributed to impurities or lattice imperfections and not to the presence of the ferroelectric phase, providing indication that the para-to ferroelectric phase transition occurs below 25 K.     

Raman spectra of forsterite and fayalite at high pressures and room temperature

Abstract

Raman spectra of the two pure end-members of olivine (forsterite and fayalite) were studied at high pressures and room temperature in a diamond-anvil cell using both single-crystals and polycrystalline samples in pressure mediums of either an ethanol-methanol mixture or H₂O. Variations with pressure were studied up to 170kbar for fayalite and to 300kbar for forsterite. Two intensive Raman bands of fayalite were definitely observable at high pressures, but only one of them can be reliably determined. Both have a linear variation within experimental uncertainty. Because of interference from the high spectral background, we found that nearly all the weak bands of forsterite could not be reliably determined at high pressures. However, the pressure variations of all bands of forsterite which can be reliably determined are non-linear. The rates of frequency change for the intense bands of forsterite determined in the present experiment are consistent with those of natural forsterites determined by Besson et al. ¹ and Gillet et al. ², but are in a slight discordance with those reported by Chopelas³. Furthermore, there is no evidence for the olivine ? spinel phase transition occurring at room temperature.     

Raman phonon spectra and lattice dynamics of 9,10-dinitroanthracene under pressure

Abstract

Raman phonon spectra of 9, 10-dinitroanthracene have been recorded in the pressure range 0-6GPa. No phase transition is detected up to the maximum pressure studied. Quasi Harmonic Lattice Dynamics calculations, based on an atom-atom potential previously modeled on homologous 9,10-disubstituted anthracenes, have been performed. The optimized potential was used to calculate the equilibrium geometry and the lattice phonon frequencies as a function of pressure. The calculated structure at ambient conditions closely resembles the experimental one. The calculated phonon frequencies show a good agreement with the experimental values at all pressures measured.     

一种新的恶二唑衍生物在金刚石对顶砧中的电阻率随压力和温度的变化关系

利用金刚石对顶砧测量了恶二唑衍生物微晶, 1,4-bis[(4-methyloxyphenyl)-1,3,4-oxadiazolyl]- 2,5-bisheptyloxyphenylene (OXD-2), 电阻随压力和温度的变化关系，并利用有限元分析方法计算了样品的电阻率。实验中，测量压力和温度达到了16 GPa和150℃。样品的电阻率随着温度的升高而降低，说明样品表现出半导体传导特性。在90-100 ℃之间，样品的电阻率有一明显的下降，说明这时发生了温度诱导的相变。随着压力的增加，样品的电阻率在6GPa左右达到最大值，此后随着压力的增加而下降。结合原位x光数据，在6GPa左右的电阻突变应该是由于样品在压力的诱导下发生了无序化的相变。     

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.     

Spectral properties of 1,3,4-oxadiazole derivatives in binary solvent mixtures

The influence of nonspecific intermolecular interactions on the fluorescence band shift of 1,3,4-oxadiazole derivatives has been investigated in the binary solvents hexane-ethanol, toluene-ethanol, toluene-acetonitrile, and carbontetrachloride-2-propanol. The dependences obtained have been analyzed in terms of preferential solvation. It has been shown that the maximum solvation energy for slightly polar compounds occurs in toluene-ethanol, toluene-acetonitrile, and carbontetrachloride-2-propanol. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 75, No. 2, pp. 177–181, March–April, 2008.     

A high pressure Raman study of TeO2 to 30 GPa and pressure-induced phase changes

The effect of pressure on the Raman modes in TeO₂ (paratellurite) has been investigated to 30GPa, using the diamond cell and argon as pressure medium. The pressure dependence of the Raman modes indicates four pressure-induced phase transitions near 1 GPa, 4.5 GPa, 11 GPa and 22 GPa. Of these the first is the well studied second-order transition fromD ₄ ⁴ symmetry toD ₂ ⁴ symmetry, driven by a soft acoustic shear mode instability. The remarkable similarity in the Raman spectra of phases I to IV suggest that only subtle changes in the structure are involved in these phase transitions. The totally different Raman spectral features of phase V indicate major structural changes at the 22GPa transition. It is suggested that this high pressure-phase is similar to PbCl₂-type, from high pressure crystal chemical considerations. The need for a high pressure X-ray diffraction study on TeO₂ is emphasized, to unravel the structure of the various high pressure phases in the system.     

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.     

单壁碳纳米管的高压拉曼研究

采用金刚石对顶砧装置对直径分布在1.3 nm左右的单壁碳纳米管进行了高压拉曼光谱研究.实验结果表明随压力的增加碳管的截面形状发生了由圆到椭圆再到扁平的变化,这和我们之前的研究结果一致.从31 GPa卸压至常压后碳管的结构得到了较好的保持,这个压力值明显高于传统的Sp2键结构的碳材料所能稳定存在的压力范围(20 GPa以...     

Raman spectra for hydrogen hydrate under high pressure: Intermolecular interactions in filled ice Ic structure

Raman studies of a high-pressure structure of hydrogen hydrate, a filled ice Ic structure, were performed using a diamond anvil cell in the pressure range 3.2-44.1 GPa. The Raman spectra of a vibron revealed that extraction of hydrogen molecules from the filled ice Ic structure occurred above 20 GPa. In addition, the Raman spectra of a roton revealed that a rotation of hydrogen molecules in the filled ice Ic structure was suppressed at around 20 GPa and then the rotation recovered, and the rotation of hydrogen molecules was suppressed again above 35.5 GPa. These results indicate that intermolecular interactions increased between guest hydrogen molecules and host water molecules at around 20 and 35.5 GPa. These intermolecular interactions were considered to be induced to stabilize the filled ice Ic structure. Above 40 GPa, symmetrization of hydrogen bond was considered to contribute to the stability of hydrogen hydrate.     

A scanning fluorescence spectroscopy of decorin under high pressure

High pressure processing is able to tenderize not only meat but also intramuscular connective tissue, which is mainly composed of collagen. Decorin, one of the proteoglycans, binds to and stabilizes collagen fibrils. It has been suggested that structural weakening of intramuscular connective tissue may result from the disappearance of the decorin–collagen interaction. In this study, the fluorescence spectra and the surface hydrophobicity of decorin molecules were measured under high pressure in order to examine the resulting change in the tertiary structure. The fluorescence intensity and the surface hydrophobicity of decorin molecules both decreased with increasing applied pressure and with applied time at the constant applied pressure, respectively. The observations indicate that the native structure of decorin is maintained during 200 MPa pressurization for less than 30 min.     

A novel four-component reaction for the synthesis of disubstituted 1,3,4-oxadiazole derivatives

The 1:1 imine intermediate generated by the addition of benzyl amine to cyclobutanone is trapped by (N-isocyanimino)triphenylphosphorane in the presence of an aromatic carboxylic acid leads to the formation of the corresponding iminophosphorane intermediate. Disubstituted 1,3,4-oxadiazole derivatives are formed via intramolecular aza-Wittig reaction of the iminophosphorane intermediate. The reactions were completed in neutral conditions at room temperature. The disubstituted 1,3,4-oxadiazole derivatives, were produced in excellent yields.     

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)。     

Diamond and cubic boron nitride under high pressure: Raman scattering,equation of state and high pressure scale

Abstract

The development of the diamond-anvil cell has stimulated Raman-scattering investigation of vibrational modes in covalent crystals. The linear pressure coefficient reported for diamond by Hanfland et at' (2.90 ± 0.05 cm-¹/GPa) agrees to within mutual experimental error with the result of Boppard et aL² (2.87±0.01 cm-¹/GPa). As to cubic boron nitride, the only work by Sanjurjo ef aL3 reports 3.45 ± 0.07 cm-¹/GPa for LO- and 3.39 ± 0.08 cm-¹/GPa for TO- modes. Since no compressibility data are availablel^1?3, the mode Griineisen parameter γ = ‐ δ In γ/δ is defined as y = K/Y·dv/aP and depends on the bulk modulus K and the calibration of the ruby scale. The above papers report y= 0.96 and y=0.95±O.O3fordiamondand γ_Lo=1.21,γTo=1.51 forBN.     

Resonance Raman spectroscopy of carbon nanotubes: pressure effects on G-mode

We use 488 and 568 nm laser Raman spectroscopy under high pressure to selectively follow evolution of Raman G-mode signals of single-walled carbon nanotubes (SWCNTs) of selected diameters and chiralities ((6, 5) and (6, 4)). The G-mode pressure coefficients of tubes from our previous work are consistent with the thick-wall tube model. Here we report the observation of well-resolved G-minus peaks in the Raman spectrum of SWCNTs in a diamond-anvil cell. The pressure coefficients of these identified tubes in water, however, are unexpected, having the high value of over 9 cm^?1 GPa^?1 for the G-plus and the G-minus, and surprisingly the shift rates of the same tubes in hexane have clearly lower values. We also report an abrupt increase of G-minus peak width at about 4 GPa superposed on a continuous peak broadening with pressure.     

Raman studies of the high pressure effects in high Tc superconductors

Abstract

The effect of a hydrostatic pressure (up to 6GPa) on the Raman spectra of YBa₂Cu₃O_x(x = 6.5 and overdoped) single crystals is investigated in the temperature range 77-300 K in connection with all available data in the literature for the other oxygen concentrations. All five strong modes (4A_g+1B_1g) are examined for both oxygen doping and compared with previously published results. From the systematic investigation of the phonon spectral characteristics with the application of pressure, the formation or disappearance of the phases is examined. The results provide a spectroscopic support for the changes induced by the hydrostatic pressure on the chain ordering and the corresponding phases.     

Effect of uniaxial pressure on the Raman spectra of fluoro perovskites containing manganese with sodium or potassium

ABSTRACT

Perovskite structured mixed metal fluorides containing manganese/sodium or potassium have been synthesized in pure form by a greener precipitation route and characterized by high-resolution powder X-ray diffraction and Raman spectroscopy techniques. While all the reflections in the powder X-ray diffraction pattern of potassium manganese fluoride could be indexed in cubic symmetry with a = 4.1889 Å, sodium manganese fluoride showed reflections at positions typical of orthorhombic symmetry (Pnma space group) with a = 5.751, b = 8.008, and c = 5.548 Å. Potassium manganese fluoride in powder form showed bands at 209, 291, 386, 558, 621, and 733 cm^?1 in the Raman spectrum at room temperature. All these bands disappeared and second-order band at 1151 and 1298 cm^?1 emerged when the powders were compacted under pressure ranging between 1 and 4 tons (uniaxial). A similar change was noticed for sodium manganese fluoride in which bands at 1099, 1149, 1203, and 1286 cm^?1 were observed for the compacted samples. The response of the vibrational modes of these compounds to uniaxial pressure revealed the existence of large structural disorder in them. Additionally, the need for the extreme care to collect and interpret Raman data of polycrystalline samples of these systems has been illustrated through this study.