Rayleigh-ritz calculation of the resonant modes of a solid parallelepiped in a pressurizing fluid

Resonant ultrasound spectroscopy relies on comparisons of experimentally determined vibrational spectra to theoretically computed spectra for the extraction of the elastic moduli of the solid samples. To determine the pressure dependence of these moduli, resonant spectra are taken for samples pressurized by a surrounding gas and knowledge of the contribution of the surface loading of the sample by the gas is needed in order to extract the intrinsic pressure dependence of the moduli. To facilitate the required comparisons, a Rayleigh-Ritz variational calculation of the vibrational spectrum is formulated which includes the loading of the solid by the pressurizing fluid. This formalism is used to compute the effect of gas loading on the vibrational spectrum of an isotropic, solid parallelepiped.     

Relaxing local modes and the theory of low-frequency Raman scattering in glasses

Raman scattering in glasses is investigated theoretically. The experimental Raman spectra of glasses exhibit a low-frequency peak (at ～10 cm^?1) that, as a rule, is attributed to vibrational modes of nanometer-sized structural units (nanocrystallites). It is established that the elastic moduli of nanocrystallites must necessarily be dependent on their sizes due to the Laplace pressure effect. A theory of the low-frequency peak is constructed using a realistic size distribution function of nanocrystallites with allowance made for the Laplace pressure effect and the dissipation of vibrational energy. Within this theory, the shape of the low-frequency peak and its evolution with temperature can be analyzed quantitatively. The proposed approach offers a physical interpretation of the experimental data and provides insight into the relation of the characteristic nanocrystallite sizes to the elastic moduli and surface tension coefficients of materials.     

The pressure and temperature derivatives of the elastic moduli of lithium hydride

The pressure and temperature derivatives of the elastic moduli of single crystal LiH have been determined at room temperature, by the ultrasonic pulse echo method. From the pressure data, the mode Grüneisen parameters as well as the low and high temperature limiting values of the Grüneisen constant were computed; the latter were only slightly different. An equation of state has been constructed for LiH, and found to be in agreement with the experimental data. Based on a non-central force model, the values of the elastic moduli and their pressure derivatives have been calculated theoretically, and the latter values compared with the experimental data.     

Study of phase transformation and elastic properties of ThX (X = N,P, As and Sb) under high-pressure

An improved interaction potential model (IIPM) has been formulated to theoretically predict the pressure induced phase transition, elastic properties and thermophysical properties of thorium monopnictides (ThX; X = N, P, As and Sb). The phase transition pressures and volume drop obtained from this model show a better agreement with the available experimental than theoretical results. We have achieved elastic moduli, anisotropy factor, Poisson's ratio, Kleinman parameter, shear and stiffness constants on the basis of the calculated elastic constants. To know the anharmonic properties, we have also computed the third-order elastic constants, first-order pressure derivatives of second-order elastic constants and thermophysical quantities. Our results are in reasonable agreement with available measured and others reported data which supports the validity of model.     

3-氨基-2,5-二氯苯甲酸振动光谱的密度泛函研究

为了本质地把握3-氨基-2,5-二氯苯甲酸(3A2,5DBA)的振动光谱和结构间的关系,在HF和B3LYP水平上利用6-311G(d,p)基组对3A2,5DBA进行了结构优化和振动频率的计算,得到了3A2,5DBA的结构信息和全部45个简正振动模式.通过与苯甲酸的结构参数以及相关文献数据的对比,发现B3LYP/6-311G(d,p)方法较HF/6-311G(d,p)方法能给出更加合理的结果.考虑到计算模拟分子和实验测量样品间的差异,对计算所得到的频率进行了合理的标度修正.在B3LYP/6-311G(d,p)方法下,对波数小于800cm-1的振动频率,标度因子取1.001 3,而波数大于800 cm-1的标度因子取0.961 3.借助Gaussian View程序包对所计算得到的振动模式进行了高精度指认,对3A2,5DBA的主要官能团及取代基团进行了振动分析.通过和实验测量的FTIR数据的比对,发现经标度修正后的计算结果和实验测量符合的很好.同时结合相关的文献报道,表明所做的振动指认和振动分析是合理的.     

Elastic interaction of point defects with dislocations

Elastic interaction between dislocation and point defects with spherical symmetry is investigated theoretically by means of the sphere-in-hole model. The interaction energy due to the different elastic moduli of the point defect and matrix is computed and then added to the interaction energy due to the size effect. The force on and the probable position of the point defect is determined. The numerical results for some selected solute atoms are computed by means of available experimental data.The results are compared with other recent papers and some experimental applications are briefly discussed.The author is much indebted to F. Kroupa, CSc., for fruitful discussions and valuable comments.     

大气压下石英毛细管内氩等离子体放电的发射光谱诊断

在长度为20 cm的石英毛细管内利用两个边缘锋利的中空的针型电极之间的氩气放电产生了高电子密度的大气压等离子体。利用发射光谱对所获得的等离子体的几个重要参数进行了诊断。利用计算机谱线拟合法合成了300 nm附近OH(A-X)的(0-0)转动谱带并通过与测量谱线的比较确定了等离子体的气体温度,根据H_β谱线Stark展宽法计算了等离子体的电子密度,采用玻尔兹曼曲线斜率法依据测得的有关氩的发射光谱估算了等离子体的电子温度。研究结果表明,这种石英毛细管内弧光放电等离子体的气体温度约为(1 100±50)K;电子密度数量级在1014 cm-3;电子温度约为(14 515±500)K。     

The spectral structure of the low level excitation in the process of the collisionless dissociation of polyatomic molecules

The resonant characteristics of the energy absorbed by SF₆ gas which is deeply cooled and exposed to IR laser irradiation of moderate intensity have been investigated experimentally. It was found that the gas cooling changes the dependence of the absorbed energy on the laser intensity and allows to reveal the structure of the spectrum. The experimental results are explained by a dominating influence of the two-photon absorption on the excitation of low vibrational levels in the laser fields of moderate intensity.     

稀土盐水溶液单泡声致发光中的特征光谱

在溶有稀有气体的稀土盐氯化铽水溶液中进行了单泡声致发光光谱的研究. 在固定驱动超声频率、不同驱动声压下, 观察到了一系列OH自由基从第一激发态A²∑⁺到基态X²Π 各振动能级跃迁所产生的谱线, 包括波长307 nm处的(0, 0)跃迁谱线, 335 nm处的(0, 1)跃迁谱线以及276 nm处的(1, 0) 跃迁谱线等. 实验结果表明较高的驱动声压有利于 276 nm处谱线的产生, 而较低的驱动声压则有利于 307 与 335 nm 处谱线的产生. 通过定义线状光谱与连续谱的光强比, 定量地表征了线状光谱在总光谱中的相对强度, 并给出了驱动声压对各跃迁谱线光强比的影响. 关键词： 单泡声致发光 驱动声压 线状光谱 光强比     

Far-Infrared spectroscopy of isolated transition metal clusters

The vibrational far-infrared (IR) spectra of isolated metal clusters in the gas phase can be measured by performing photo dissociation spectroscopy of their rare gas complexes. For these experiments an intense and widely tunable source of far-IR radiation is required, and the Free Electron Laser for Infrared eXperiments (FELIX) is ideally suited for this. Vibrational spectra are obtained for vanadium cluster cations as well as for neutral and cationic niobium clusters. The comparison of the experimental vibrational spectra with theoretically calculated spectra allows for the determination of the structure of the metal clusters.     

Theoretical study of the photoelectron spectrum of ethyl formate: Ab initio and density functional theory investigation

The first ionization energy and associated photoelectron spectrum of ethyl formate are investigated with quantum chemistry calculations. The geometries, harmonic vibrational frequencies and first ionization energy are computed at the Hartree-Fock (HF) and at the second order Møller-Plesset perturbation theory (MP2). Moreover, accurate ionization energies are obtained with the Coupled-Cluster theory including singles and doubles excitations (CCSD) as well as singles, doubles and perturbative triples excitations (CCSD(T)). Then, these ab initio results are assessed with respect to experimental values. Additionally, the ionization energies are also calculated with the computationally attractive density functional theory (DFT). In this case the accuracy of several exchange-correlation functionals is evaluated by comparison with the ab initio and experimental results. In a next step, the vibrational structure of the photoelectron spectrum is simulated at the HF, MP2 and DFT levels via the calculation of the Franck-Condon factors. These simulations are compared to the experimental photoelectron spectrum and allow an accurate reproduction of the vibrational progression.     

Effective elastic moduli under hydrostatic stress—I. quasi-harmonic theory

Fourth-order finite strain expressions for the effective elastic moduli of a solid under hydrostatic stress are derived from a general expression for effective elastic moduli. Expressions in terms of the strain tensors E and η are given. The expressions are then written in terms of the moduli and their pressure derivatives evaluated at an arbitrary reference state. The temperature dependence of these expressions is derived from the fourth-order quasi-harmonic expression for the lattice vibrational energy. Some general thermodynamic relations are derived between the parameters which specify the thermal effects and the pressure and temperature derivatives of the elastic moduli at the reference state. General relations between isothermal and isentropic elastic moduli and their pressure and temperature derivatives are also given. Much of the development is valid for materials of arbitrary symmetry, but the complete development is given only for materials of cubic symmetry.     

混合气体声复合弛豫频谱的解析模型

为研究声传播和分子多模式振动能量弛豫的相互关系,本文提出了一种混合气体声 复合弛豫频谱的解析模型.该模型从振动模式微观能量转移及其耦合形成宏观弛豫过程两个角度, 分析了依赖于声频率的混合气体有效热容.并通过求解振动模式能量转移的通用弛豫方程, 最终得到可同时体现主副弛豫过程的声弛豫吸收和声频散的解析结果.仿真结果表明, 对于CO₂, CH₄, N₂和O₂组成的多种混合气体, 该模型的声吸收谱与实验数据相符,峰值误差在1%以内,且反映了多振动模式形成的 声复合弛豫吸收谱上通常仅会显现1-2个吸收波峰的物理现象.与已有模型相比, 本解析模型可直接求出混合气体声弛豫频谱上特征点的解析形式,并利于对其进行定性定量分析. 从而为研究声传播特性与气体分子弛豫特性的相互关系提供了一个有效理论模型.     

Glow Discharge Characteristics of Hollow Needle-Plate Electrode in Atmospheric Pressure ArgonSCIEI北大核心CSCD

Atmosphere pressure uniform plasma has the broad application prospect in the industrial field. Using hollow needle cathode - plate anode device excited by direct-current voltage, a uniform and stable glow discharge is generated at atmospheric pressure in ambient air with argon used as working gas. The influence of the experimental parameters (including gas flow rate and the gas gap width) on discharge has been investigated by optical method. It can be found that a glow-discharge plasma column can bridge the two electrodes. The plasma column is uniform, and no filaments can be discerned. Near the plate electrode, the diameter of the plasma column is largest of all positions. The maximal diameter of the plasma column increases with increasing the discharge current or the gas flow rate. Through electrical method, the voltage-current characteristic has been investigated. It has been found that the discharge voltage decreases with increasing the current which is similar with the characteristic of glow discharge in low pressure. It increases with increasing the gas gap width or the gas flow rate. By analyzing the optical emission spectrum scanning from 330 to 450 nm emitted from the direct-current glow discharge, the molecular vibrational temperature and the intensity ratio of spectral lines I-391.4/I-337.1 have been investigated as functions of the gas flow rate and gas gap width. Results indicate that both the vibrational temperature and the intensity ratio of spectral lines I-391.4/I-337.1 decrease with increasing the gas flow rate or the gas gap width. In addition, the molecular vibrational temperature and the intensity ratio of spectral lines I-391.4/I-337.1 have been investigated in spatial resolution along the direction of gas flow(plasma column axial), and give a qualitative analysis as well. It is found that the vibrational temperature and the average electron energy increase with increasing the distance from the hollow needle cathode. These results are important to the industrial applications of glow discharge.     

Dispersion interactions and vibrational effects in ice as a function of pressure: a first principles study

We present a first principles theoretical framework that accurately accounts for several properties of ice, over a wide pressure range. In particular, we show that, by using a recently developed nonlocal van der Waals functional and by taking into account hydrogen zero point motion, one can properly describe the zero temperature equation of state, the vibrational spectra, and the dielectric properties of ice at low pressure and of ice VIII, a stable phase between 2 and 60?GPa. While semilocal density functionals yield a transition pressure from ice XI to VIII that is overestimated by almost an order of magnitude, we find good agreement with experiments when dispersion forces are taken into account. Zero point energy contributions do not alter the computed transition pressure, but they affect structural properties, including equilibrium volumes and bulk moduli.     

空心针-板电极大气压氩气辉光放电的特性研究

大气压均匀放电等离子体在工业领域具有非常广泛的应用前景,它是利用直流电源激励的空心针-板放电装置,以氩气为工作气体在大气压空气中产生均匀稳定的放电。对氩气流量和气隙间距对辉光放电发光特性的关系进行了研究,结果表明放电所产生的等离子体柱连接两个电极,发光较为均匀(观察不到放电丝)。在板电极附近放电等离子体柱直径最大,最大直径随着电流和气流的增大而增大。放电伏安特性研究发现,与低气压辉光放电相类似,两电极间的电压随着电流的增大而减小,并且随气流和气隙间距的增大而增大。对该大气压直流均匀放电在扫描范围为330～450 nm的光学发射光谱进行分析,获得了放电等离子体的分子振动温度和谱线强度比I_391.4/I_337.1随氩气流量和气隙间距的变化关系。I_391.4/I_337.1均随流量和气隙间距的增大而降低。对等离子体柱的I_391.4/I_337.1沿气流方向(等离子体柱轴向)进行了空间分辨测量,并进行了定性分析,结果表明,振动温度及电子平均能量随着远离空心针口距离的增大而增大。这些结果对大气压辉光放电在工业中的应用具有重要意义。     

Energy exchange in high-pressure discharge plasmas excited in diatomic gases

The energy loss that electrons sustain in inelastic collisions in high-pressure discharge plasmas excited in molecular gases is strongly affected by the vibrational temperature of the molecules and the temperature of the neutral gas. The theoretically computed average fractional energy loss due to collision with a gas molecule is far higher than the respective experimental values available at present. The energy exchange occurring between the various components of a discharge plasma is also influenced to a considerable degree by the processes of electronic and molecular vibrational de-excitation.The author wishes to extend his thanks to Prof. Dr. V. Truneek, CSc., for valuable comments, to Mr. R. Nekuda for the preparation of the diagrams, and to Mr. J. Dvoák for the automatic computer programme of the calculations.     

不同时空结构的四边形放电斑图等离子体参量研究

采用发射光谱法,研究了不同时空结构四边形斑图的等离子体参量。实验发现,在低气压区和高气压区,四边形斑图表现出不同的时空结构。利用N₂分子第二正带系的六条谱线强度计算了分子振动温度;利用第一负带系N+₂(391.4 nm)与第二正带系N₂(394.1 nm)谱线强度比,研究了电子能量的变化;利用Ar原子696.54 nm谱线的展宽和频移来反映电子密度;利用Ar原子特征谱线强度比法计算了电子激发温度。结果表明：低气压区四边形斑图的分子振动温度、电子激发温度和电子平均能量均大于高气压区四边形斑图,而电子密度小于高气压区四边形的电子密度。     

The influence of hydrostatic pressure on the static and dynamic properties of an InSe crystal: A first-principles study

The pressure dependences of the crystallographic parameters of the γ-InSe structure in the range up to 15 GPa are theoretically investigated using the density-functional method. It is established that, in the range from 7 to 11 GPa, the pressure dependences of the lattice parameters exhibit an anomalous behavior: the rigidity of the lattice increases in the direction of the weak bond and decreases in the plane of the layers. The layer thickness is characterized by a nonmonotonic pressure dependence. The numerical values of the lattice parameters of the crystal structure under compression are determined, and the pressure dependences of the vibrational frequencies at the center of the Brillouin zone are calculated theoretically. The results of the theoretical calculations are in good agreement with the available experimental data.     

基于振动拉曼散射的差分水Ring效应系数卷积计算模型

利用被动差分吸收光谱算法反演水体上方尤其是海洋上方的大气痕量气体浓度时, 水体的振动拉曼散射导致对太阳光谱中夫琅禾费线的填充.若不考虑这种类似大气Ring效应的水Ring效应, 会直接影响反演精度. 参考OMI传感器对大气Ring效应校正的卷积算法, 针对痕量气体OClO的反演, 利用经过大气消光计算后的太阳 360–400 nm入射光谱和对应波段的水体后向振动拉曼散射系数,通过卷积差分计算,得到了差分水 Ring效应系数. 与Vasilkov模型计算得到的结果比较,二者的相关系数R 达到0.9665. 关键词： 水Ring效应 振动拉曼散射 卷积 被动差分吸收光谱算法