Raman spectra and phase composition of MnGeO3 crystals

MnGeO₃ single‐crystal samples have been synthesized by optical zonal melting and spontaneous crystallization. X‐ray crystal analysis showed the first sample to be a two‐phase one with phase ratio as follows: 17% – monoclinic C2/c, and 83% – orthorhombic Pbca; the phase ratio of the second sample was unknown. Raman spectra have been produced for these samples. Lattice dynamics has been simulated and polarization dependencies of lines' intensities have been analyzed to interpret experimental Raman spectra and to attribute lines to the spectra of monoclinic and orthorhombic phases. Copyright © 2015 John Wiley & Sons, Ltd.     

Polarized Raman scattering and lattice eigenmodes of antiferromagnetic NdFeO3

The first‐ and second‐order Raman‐active phonons in the orthorhombic Pbnm NdFeO₃ single crystals were studied by means of polarized Raman scattering and lattice dynamics computations (LDC). The zone‐center phonons of A_g symmetry were distinguished from the B_1g eigenmodes by performing polarized Raman scattering experiments using two parallel polarization configurations, X′(ZZ)X′ and Z(X′X′)Z. With the help of LDC, we were able to assign most of the observed Raman‐active modes, including phonons of B_2g and B_3g symmetry. The LDC results indicated that among the 16 force constants employed, the one corresponding to the stretching vibration between the central Fe cation and the axial oxygen atom in a FeO₆ octahedron unit had the largest value. This suggests that the B‐site Fe cation is more tightly bound to the axial O1 ion than the other two equatorial O2 ions. It was further shown that at higher wavenumbers, the displacement of oxygen atoms contributed dominantly to the zone‐center vibrations. Copyright © 2008 John Wiley & Sons, Ltd.     

First-principles study of lattice dynamics and thermodynamics ofosmium under pressure

We have performed the first-principles linear response calculations of the lattice dynamics, thermal equation of state and thermodynamical properties of hcp Os metal by using the plane-wave pseudopotential method. The thermodynamical properties are deduced from the calculated Helmholtz free energy by taking into account the electronic contribution and lattice vibrational contribution. The phonon frequencies at Gamma point are consistent with experimental values and the dispersion curves at various pressures have been determined. The calculated volume, bulk modulus and their pressure derivatives as a function of temperature are in excellent agreement with the experimental results. The calculated specific heat indicates that the electronic contribution is important not only at very low temperatures but also at high temperatures due to the electronic thermal excitation. The calculated Debye temperature at a very low temperature is in good agreement with experimental values and drops to a constant until 100~K.     

Directional dependence of the phonon modes in biaxial sodium nitrite

The directional dependence of the phonon mode frequencies is calculated in the three principal planes of biaxial sodium nitrite at 7 and 300 K, using the lattice mode parameters determined from the simulation of the infrared reflectivity spectra polarised along the three cristallographic axes. Good agreement is obtained between the calculated and experimental infrared reflectivity spectra for different orientations of the wave vector in the a-c plane of sodium nitrite.     

Lattice dynamics of tetragonal Nd2BaZnO5

A short‐range force constant model (SRFCM) has been applied to investigate the Raman and the infrared wavenumbers in Nd₂BaZnO₅ in its tetragonal phase of space group I4/mcm. Calculations of zone‐center phonons are made with five stretching and five bending force constants. All the Raman and infrared values are then assigned to their corresponding modes. Two Raman modes are reassigned on the basis of group theoretical calculations. The calculated Raman wavenumbers exhibit good agreement with the observed values. Copyright © 2007 John Wiley & Sons, Ltd.     

High pressure lattice dynamics, dielectric and thermodynamic properties of SrO

Using density functional theory and density functional perturbation theory we have studied the effects of hydrostatic pressure on lattice dynamics, dielectric and thermodynamic properties of the rocksalt (NaCl) and CsCl phases of SrO. The stability of the NiAs type structure, experimentally confirmed to be stable in BaO, is also investigated. Studying the lattice dynamics of the NaCl and CsCl phases at various pressures, in the range of the phase stability, we have found the lattice dynamical instabilities which govern the phase transitions between NaCl and CsCl phases with increasing and decreasing pressure. By monitoring the behaviour of the found soft modes, we have calculated the transition pressures upon compression and decompression of SrO crystal. Lattice dynamics calculations reveal that the rocksalt and CsCl structures are unstable with respect to the soft transversal acoustic modes at single points of the Brillouin zone, which points to the fact that the transitions are of displacive type. Responses to electric fields and thermodynamic properties at high pressures are also given and discussed. All our results are in a good agreement with experimental data where applicable.     

Phonon dispersion and Raman spectra of wurtzite InAs under pressure

The authors have systematically studied the vibrational properties of wurtzite InAs at high pressure within the Density Functional Theory scheme. It is found that pressure significantly affects the phonon dispersion curves and Raman spectra. We observed an indication of phase transition for WZ-InAs at about 10 GPa. The elastic constants calculation show mechanical stability for WZ-InAs. The calculated values of structural parameters are in good agreement with available data. There is a quadratic increase in optical modes with pressure while the LO–TO splitting and effective charge decrease linearly with pressure.     

用拉曼光谱测量离子注入引起的晶格应变

 对于10个周期的AlAs/GaAs超晶格和25个周期的GaAs/Ga0.92In0.08As超晶格,在室温下进行0.28 MeV的Zn＋注入,注入剂量为5×10¹³~5×10¹⁴ cm^-2。通过拉曼光谱测量,定量地分析了由于离子注入所引起的晶格内应变。实验结果表明：在所选用的注入剂量下,由于离子注入引起的应变小于体材料GaAs的最大非驰豫应变值0.038,说明该注入条件下,注入区的结晶态仍然保持得比较好。在较高注入剂量下应变达到饱和,说明缺陷的产生和复合达到了平衡,从而形成了均衡的应变场分布。     

Inelastic neutron scattering study of lattice dynamics in α-ZnCl<Subscript>2</Subscript>

Inelastic neutron scattering experiments have been carried out to measure the phonon density of states in polycrystalline α-ZnCl₂ at Dhruva, Trombay. Lattice dynamical calculations, based on an interatomic potential model, are accomplished to study phonons associated with this otherwise extremely hygroscopic compound. Our calculated data are found to be well-compatible with the available measured ones.     

Raman spectra of CdS nanocrystals in Nafion: longitudinal optical and confined acoustic phonon modes

Quantum confinement effects on the longitudinal optical and acoustic phonons in CdS nanocrystals in the strongly confined regime in the polymer matrix Nafion are studied using Raman spectroscopy. The LO-phonon modes show size-dependent asymmetric broadening though the broadening and asymmetry are less than those predicted by the phonon confinement models. Two types of confined acoustic modes corresponding to n=1, l=0 and n=1, l=2 spheroidal vibrations are observed. Softening of the spheroidal modes is observed in the strongly confined regime.     

基于拉曼频移的白宝石压腔无压标系统高温高压实验标定

在高压实验科学中, 各类宝石压腔是最为常见的高压设备之一, 其样品腔中压力的精确标定是实验的关键. 目前, 人们主要通过加入红宝石等压标物质来进行定压, 但压标物质的加入会增加实验的装样难度, 改变样品腔中的物理化学环境, 甚至直接与实验样品发生反应, 从而对实验结果产生影响. 在0–6.3 GPa和300–573 K下, 利用共聚焦拉曼显微镜, 根据白宝石压砧砧面的ν₁₂ 拉曼频移与温度和压力的变化关系, 建立了一套适用于高温高压水热体系的无压标白宝石压腔系统. 实验结果表明: 白宝石砧面的ν₁₂ 峰随着压力的升高发生线性蓝移, 而随着温度升高则发生线性红移, 且温度和压力对拉曼频移的影响存在耦合效应. 利用本实验结果, 可在高温高压下根据白宝石砧面的拉曼频移计算出样品腔的压力P=(Δλ-0.01913×ΔT)/(1.9158-0.00105×ΔT), 在物理学、材料学和地球科学等领域具有重要应用.     

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.     

Raman G‐mode of single‐wall carbon nanotube bundles under pressure

Raman studies of nanotubes under pressure have been a lively area of research. However, the results are not always as expected and at times have not been adequately explained. One example of the diversity of the results is the higher energy Raman mode (the graphitic mode, GM) shift to higher wavenumber under pressure. Here we report a new high‐pressure Raman study showing that the effects of the variation in the tube diameters and the pressure transmitting medium are both crucial for understanding the outcomes of such high‐pressure experiments. Copyright © 2011 John Wiley & Sons, Ltd.     

Lattice dynamics of lithium oxide

Li₂O finds several important technological applications, as it is used in solid-state batteries, can be used as a blanket breeding material in nuclear fusion reactors, etc. Li₂O exhibits a fast ion phase, characterized by a thermally induced dynamic disorder in the anionic sub-lattice of Li⁺, at elevated temperatures around 1200 K. We have carried out lattice-dynamical calculations of Li₂O using a shell model in the quasi-harmonic approximation. The calculated phonon frequencies are in excellent agreement with the reported inelastic neutron scattering data. Thermal expansion, specific heat, elastic constants and equation of state have also been calculated which are in good agreement with the available experimental data.     

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.     

Raman spectra of the lattice vibrations of solid nitrogen near room temperture

Abstract

Low-frequency peaks begin to appear in Raman spectra of solid N₂ when δ-N₂ transforms to either the ?- or η-N₂ phase and orientational order develops in δ-N₂. These same peaks are known at 15 K but are very much broader at the higher temperatures. Near the phase boundaries, these peaks are extremely weak and remain weak even under the best of conditions. We have used Raman spectra of these modes to map the δ-? and δ-? phase boundaries.     

高压拉曼光谱方法研究联苯分子费米共振

测量了0—15 GPa压强下联苯分子的拉曼光谱. 结果表明,随压强增加,分子内和分子间π-π共轭和离域效应增强,谱线的绝对强度变大、蓝移. 联苯分子的两费米共振谱线强度比R_f/a减少,频率差Δ增加,当压强为8 GPa时,费米共振现象消失,利用Betran理论得出了固有频率差Δ₀和耦合系数ω随压强的变化关系,通过高压下相变进行了解释,并探讨了高压下费米共振耦合变弱的机理. 关键词： 联苯 费米共振 高压 拉曼光谱     

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。