Raman study of phase transition in ferroelectric Ba0.95Ca0.05TiO3

Raman scattering investigation of phase transition in the ferroelectric Ba_0.95Ca_0.05TiO₃ is reported. The results suggest onset of significant dynamic disorder at 105°C. This corroborates findings of recent structural study regarding large positional disorder associated with Ti and O1 atoms well below the tetragonal to cubic transition temperature (∼150°C).     

A2( MoO4)3(A=Al,Cr,Fe)结构与相变的Raman光谱研究

用XRD、Raman光谱和DSC研究了Al2 (MoO4)3、Cr2( MoO4)3和Fe2 (MoO4)3的结构与相变.Al2(MoO4)3、Cr2 (MoO4)3和Fe2 (MoO4)3在室温下为单斜相,分别在483 K、673 K和783 K附近转变为正交相.发现MO4四面体的对称和反对称伸缩振动模的频率和相对强...     

Variations of phase transition temperature and enthalpy in the systems Na2Mo1− x W x O4 and Na2Mo1− y S y O4

The samples in two material systems, Na₂Mo_{1? x} W _x O₄ and Na₂Mo_{1? y} S _y O₄, were prepared by using conventional solid reactions and characterized by X-ray diffractometer (XRD), energy dispersive X-ray spectroscopy (EDX), and difference scanning calorimetry (DSC). The XRD and EDX data indicated that all the samples in both systems were in the solid solution range. The DSC data indicated that in the system Na₂Mo_{1? x} W _x O₄, the solid–solid transition temperatures increased and in the system Na₂Mo_{1? y} S _y O₄, the solid–solid transition temperatures decreased. The total enthalpy (ΔH _total) of the solid–solid transitions in the system Na₂Mo_{1? x} W _x O₄, decreased much less than that in the system Na₂Mo_{1? y} S _y O₄. This is probably because similar to Na₂MoO₄, the solid–solid transition of Na₂WO₄ has relatively large ΔH _total, but Na₂SO₄ has much smaller solid–solid transition enthalpy. In order to modify the transition temperatures of Na₂MoO₄ and also to keep its relatively large ΔH _total, it is necessary to choose a doping material with large ΔH _total.     

Splitting of optical mode in (NH_4)_2 PtBr_6 studied by Raman scattering

Ｓｐｌｉｔｔｉｎｇｏｆｏｐｔｉｃａｌｍｏｄｅｉｎ（ＮＨ＿４）＿２ＰｔＢｒ＿６ｓｔｕｄｉｅｄｂｙＲａｍａｎｓｃａｔｔｅｒｉｎｇＳｐｌｉｔｔｉｎｇｏｆｏｐｔｉｃａｌｍｏｄｅｉｎ（ＮＨ＿４）＿２ＰｔＢｒ＿６ｓｔｕｄｉｅｄｂｙＲａｍａｎｓｃａｔｔｅｒｉｎｇ￥...     

六氯铅铵晶体相变的拉曼散射研究

在５Ｋ～３００Ｋ温度范围内对六氯铅铵晶体进行了拉曼散射测量，该晶体在Ｔｃ＝７８Ｋ发生从立方结构（Ｏ＾５４）至三方结构（Ｃ＾２３ｉ）的二级相变，ＰｂＣｌ＾２－６八面体Ａ１ｇ模和ＮＨ＾＋４四面体Ａ１模的拉曼频移在Ｔｃ时出现极大值，八面体Ｔ２ｇ模，四面体Ｔ２模和外振动Ｔ２ｇ模在Ｔｃ以下发生连续分裂，另外在Ｔｃ以下观测到对应于高温相ＰｂＣｌ＾２－６八面体Ｔ１ｇ模的软模。     

金刚烷的高压拉曼光谱研究

对金刚烷（C10H16）进行了常温原位高压拉曼光谱研究,最高压力为25 GPa。通过分析高压拉曼光谱,结合拉曼频移随压力的变化情况,得出在实验压力范围内C10H16发生了多次相变。0.6 GPa时,C10H16由常温常压下的无序相（$alpha$相）转变为有序相（$beta $相）;继续加压至1.7 GPa时,第2次结构相变开始,直至3.2 GPa,第2次相变完全结束;第3次相变开始于6.3 GPa,结束于7.7 GPa;22.9 GPa时发生了第4次结构相变。另外,首次在拉曼光谱上探测到第3次相变过程中晶格振动峰的变化,说明第3次相变并非前人报道的等结构相变。     

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.     

Raman and Hyper-Rayleigh Scattering in Lithium Tetraborate Crystals

Experimental studies of Raman scattering and the infrared reflection spectra of lithium tetraborate crystals were carried out within a broad temperature range with various polarization geometries. The crystals studied are characterized by record values of radiation resistance, transparence within a broad spectral range including the ultraviolet region, and nonlinear optical properties. A group-theoretical analysis of the vibrational spectra of this crystal was performed and fundamental vibrational terms were assigned to the symmetry types of the point group as well as the polarizations of the corresponding modes. The effective Raman cross section was measured and was found to be one order of magnitude higher than those of the known crystals, in which the stimulated Raman scattering (SRS) was observed. The nonlinear optical and electrooptical coefficients were evaluated and were found to be consistent with the results of independent measurements. The effect of a drastic increase in the intensity of quasi-elastic light scattering at 253 K was registered. It was associated with the phase transition that consists of the disordering of lithium ions with respect to the rigid skeleton. The formation energy for Frenkel defects in the lithium sublattice and the activation energy of the ionic conduction when heating the sample were calculated from the obtained temperature dependences of the intensity of quasielastic and hyper-Rayleigh light scattering.     

Inelastic Light Scattering Near the Ferroelectric Phase-Transition Point in Bismuth Vanadate Crystals

The Raman and Brillouin spectra in bismuth vanadate crystals near the ferroelectric phase-transition point are studied. The intensity maximum corresponding to the soft mode in light scattering spectra is found. This mode is responsible for the instability of the bismuth vanadate crystal lattice in the vicinity of the ferroelectric phase-transition point. Strong interaction of the soft optical mode with an acoustic mode of the corresponding symmetry is revealed by an analysis of the Raman and Brillouin spectra observed. The theory of light scattering by coupled lattice modes based on the model of two strongly coupled oscillators is developed. The introduction of an additional oscillator strongly interacting with the fundamental soft mode is shown to result in a temperature shift of the structural phase transition to higher temperatures. The results obtained confirm the possibility of changing the phase-transition temperature by modification of the vibrational spectrum through introduction of additional degrees of freedom or comminution of the macroscopic sample with formation of the ordered superdispersed structure (globular crystal). These results are general and can be subsequently used to increase the phase-transition temperature in ferroelastics, ferroelectrics, and superconductors.     

非线性光学晶体的高压拉曼散射研究

 报道了高压下非线性光学晶体KNbO₃（KN）,KIO₃（KI）和KTiOAsO₄（KTA）的Raman散射研究结果,压力引起的Raman光谱非常丰富,在所有的样品中都观察到了压致相变。另外,在KN晶体中发现了非常强的压致振动耦合现象及高压非晶相。对于KTA,建立了Raman光谱变化与其倍频效率随压力提高之间的可能联系。在22 GPa以上,KI晶体的基本组成集团可能由IO₃变为IO₆。     

C_(60)高压相变的拉曼光谱研究

本文对非静水压淬火的 C_(60)样品进行了拉曼光谱研究。在14.8GPa 以上,C_(60)的1468cm~(-1)特征峰的频率和线宽保持不变,这是 fullerite 相己转变成“透明相”的拉曼光谱证据。在32GPa 以上,原 C_(60)的散射峰全部消失,只观察到两个新的弥散的弱散射峰。表明 C_(60)原子团簇已倒塌或严重畸变。     

叠氮化钠原位高压拉曼光谱研究

在室温条件下,利用金刚石对顶砧高压技术对叠氮化钠进行了原位高压拉曼光谱研究,采用红宝石荧光压标测压,实验的最高压力为37.7GPa。实验压力范围内拉曼光谱随压力增加发生了丰富的变化。由于多处拉曼峰的出现和消失并伴随频移有拐点,我们判断叠氮化钠在0~0.4GPa时发生了第一次结构相变,在相变过程中叠氮根的天平振动模式(Eg)出现了振动模式分裂为Ag和Bg,并且伴随着叠氮根离子之间的电荷转移。随着压力继续增加,在14.1GPa和27.3GPa分别发生了第二次和第三次结构相变。压致相变的路径为β-NaN_3→α-NaN_3→γ-NaN_3→δ-NaN_3。我们的拉曼散射研究,证实了此前的XRD研究。此外,结合计算,我们对常压下β-NaN_3的拉曼振动进行了指认。