Thermodynamic properties of lithium,sodium, and potassium at high pressure

The Gibbs thermodynamic potential is constructed for Li, Na, and K in the lattice vibration approximation with the aid of the Krasko-Gurskii model pseudopotential. The isothermal modulus of volume elasticity and its pressure derivative are calculated. Compression values are calculated from the equation of state d/d =0. The results obtained agree well with experiment.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 2, pp. 91–97, February, 1978.     

Ab initio calculations of the thermodynamic parameters of lithium, sodium, and potassium oxides under pressure

The parameters of the equation of state and Grüneisen parameters for lithium, sodium, and potassium oxides have been calculated in the generalized gradient approximation of the density functional theory using a linear combination of atomic orbitals with the CRYSTAL09 software package. The frequencies of long-wavelength normal mode vibrations have also been calculated and the dependence of these frequencies on the pressure has been established. The Debye temperature has been determined from the elastic characteristics of the compounds. The dependences of the Debye temperature, compressibility, thermodynamic potential, entropy, specific heat, thermal expansion coefficient, and thermal conductivity coefficient on the pressure in the range from ?3 to ?15 GPa and on the temperature have been calculated in the quasi-harmonic Debye model. The results obtained are in satisfactory agreement with the available reference and experimental data.     

金属铍热力学性质的理论研究

使用第一性原理方法结合平均场模型研究了压力从0到150GPa、温度从0到1500K，金属铍六角密排结构(hcp)的热力学性质，包括铍的常态性质，等温高压物态方程，以及常压下平衡体积、体弹模量随温度的变化，Hugoniot曲线等.0K物态方程由广义梯度近似下的密度泛函理论计算，粒子热运动的贡献由平均场模型计算.由于铍的Debye温度比较高，计算自由能时考虑了零点振动能修正.计算结果与已有的静力学和冲击波实验数据符合得非常好. 关键词： 热力学性质 物态方程 第一原理计算     

NO分子宏观气体热力学性质的理论研究

采用量子统计系综理论,研究了基态NO分子宏观气体摩尔熵、摩尔内能、摩尔热容等热力学性质.首先应用课题组前期建立的变分代数法(variational algebraic method, VAM)计算获得了基态NO分子的完全振动能级,得到的VAM振动能级作为振动部分,结合欧拉-麦克劳林渐进展开公式的转动贡献,应用于经典的热力学与统计物理公式中,从而计算得到了1000-5000 K温度范围内NO宏观气体的摩尔内能、摩尔熵和摩尔热容.将不同方法计算得到的摩尔热容结果分别与实验值进行比较,结果表明基于VAM完全振动能级获得的结果优于其他方法获得的理论结果.振动部分采用谐振子模型对无限能级求和计算热力学性质的方法有一定的局限性,应当使用有限的完全振动能级进行统计求和.     

块状NiSe2的电学，光学和热力学性质的理论研究

在密度泛函理论框架下通过平面波赝势的第一原理计算,研究了块体材料NiSe2的电学,光学和热力学性质.根据计算得到的立方晶体（空间群：PM3,No：200）的能量-体积曲线,获得了最低能量的最优结构.基于能带结构和电子态密度结构计算的结果表明,NiSe2为半金属.当有电磁波穿过块体NiSe2时,通过非自洽计算,分析介电函数的实部和虚部得到了能量损失函数谱,反射率,吸收谱,折射系数和消光系数.在准谐波德拜模型的基础上,我们还研究了NiSe2的热力学性质.     

GaP相变及热力学性质的理论研究

利用基于密度泛函理论的第一性原理方法研究了闪锌矿和氯化钠结构的GaP的相变及热力学性质.对两种结构的能量体积曲线做公切线,得到了从闪锌矿到氯化钠结构的相变压力约为26.2GPa,与实验结果一致.通过准谐德拜模型得到了不同温度下体积和热膨胀系数与压强的关系,以及不同压强下热容与温度的关系.     

Effects of uniaxial stress on dielectric properties of lithium modified potassium sodium niobate ceramics

In this work, the solid solution of ((K_0.5Na_0.5)_1−xLi_x)NbO₃ ceramics with x=0.03, 0.04, 0.05, 0.06 and 0.07 was prepared by a conventional mixed-oxide and solid-state sintering method. The structural phase formation and microstructure were characterized by X-ray diffraction technique and scanning electron microscopy. The ceramics were identified by XRD as a single-phase perovskite structure with symmetry gradually changing from orthorhombic to tetragonal. The grain size and the optimum density of the sintered ceramics were noticeably compositional-dependent. The dielectric properties of the ((K_0.5Na_0.5)_1−xLi_x)NbO₃ ceramics under the uniaxial compressive stress were observed at stress up to 180 MPa. The results showed that the dielectric constant and the dielectric loss tangent increased with applied stress. The change in the dielectric properties with stress was seen to depend on the composition and grain size. The observations were interpreted in terms of the intrinsic and extrinsic contributions to the changes in dielectric properties upon the applied compressive stress.     

The thermodynamic properties of lithium peroxide,Li2O2

Recently, Cota et al. gave an improved crystal structure of lithium peroxide. For the sake of investigation of the thermal properties for this structure of Li₂O₂, the Debye model is adopted in our work. This model combines with the ab initio calculations within local density approximation (LDA) using pseudopotentials and a planewave basis in the framework of density functional theory (DFT), and it takes into account the phononic effects within the quasi-harmonic approximation. We find that our calculated lattice constant using this model is in excellent agreement with the data from Cota et al. Based on the first principles study and the Debye model, the thermal properties including the equation of state, the Debye temperature, the heat capacity and the thermal expansion are obtained in the whole pressure range from 0 to 10 GPa and temperature range from 0 to 500 K.     

钛乙烯储氢材料的热力学和动力学性质研究

之前的工作中已经预测了钛乙烯（C2H4Ti）储氢的几何结构,本文将继续利用密度泛函理论（DFT）和B3LYP杂化密度泛函方法来计算之前预测出的C2H4Ti(H2)n结构中的C2H4Ti和H2反应的焓变和自由能变。通过焓变和自由能变的计算结果,可以看出：钛乙烯在298K、250K、200K下可以稳定的吸附5个氢分子,同时放出大量的热量,生成的C2H4Ti(H2)n化合物在常温下也具有热力学稳定性。此外,本文通过Gaussian03中的伯恩近似分子动力学（BOMD）方法计算了C2H4Ti(H2)5化合物在298K、250K、200K三个温度下的动力学性质。通过动力学研究的结果,可以发现钛乙烯分子在常温298K下储氢时间不长;同时得到钛乙烯分子在200K下能长时间稳定吸附五个氢分子,这进一步表明降低温度对钛乙烯分子稳定储氢是有利的。     

钛乙烯储氢材料的热力学和动力学性质研究

之前的工作中已经预测了钛乙烯(C_2H_4Ti)储氢的几何结构,本文将继续利用密度泛函理论(DFT)和B_3LYP杂化密度泛函方法来计算之前预测出的C_2H_4Ti(H_2)_n结构中的C_2H_4Ti和H_2反应的焓变和自由能变.通过焓变和自由能变的计算结果,可以看出:钛乙烯在298 K、250 K、200 K下可以稳定的吸附5个氢分子,同时放出大量的热量,生成的C_2H_4Ti(H_2)_n化合物在常温下也具有热力学稳定性.此外,本文通过Gaussian03中的伯恩近似分子动力学(BOMD)方法计算了C_2H_4Ti(H_2)_5化合物在298 K、250 K、200 K三个温度下的动力学性质.通过动力学研究的结果,可以发现钛乙烯分子在常温298 K下储氢时间不长;同时得到钛乙烯分子在200 K下能长时间稳定吸附五个氢分子,这进一步表明降低温度对钛乙烯分子稳定储氢是有利的.     

Theoretical study of elastic and thermodynamic properties of CuSc intermetallic compound under high pressure

The structural, mechanical and thermodynamic properties of copper scandium CuSc intermetallic compound under temperature and pressure have been investigated using the plane wave (PW) - pseudopotential (PP) approach in the framework of the density functional theory (DFT). The structural parameters at equilibrium, the elastic moduli, the mechanical stability criteria and the sound velocity are studied in the pressure range 0–12 GPa. In addition, the heat capacity, the Grüneisen parameter, the Debye temperature, the entropy, and the thermal expansion coefficient are studied for temperatures ranging from 0 up to 1000 K. The equilibrium lattice parameter found is around 3.261 Å. It is in good agreement with the experimental one of 3.25 Å reported in the literature. According to the generalized elastic stability criteria, we predict the occurrence of a phase transition of the B2-type structure at 25.5 GPa. At room temperature and zero-pressure, the isothermal bulk modulus and the Grüneisen parameter found were 80.86 GPa and 2.04 respectively.     

The infrared absorption spectra and structure of some simpler alkoxides of lithium,sodium and potassium

The infrared absorption spectra of the crystalline methoxides of lithium, sodium and potassium and their deuterated derivatives, as well as the ethoxides of lithium and sodium, have been measured in the 2–25m region and interpreted. It has been shown that the successive displacement of the C-H (C-D) stretching frequencies to the longwave region, on passing from methanol to the methoxides of lithium, sodium and potassium, is determined by the differences in the nature of the O-H, O-Li, O-Na, and O-K bonds. The stretching frequency displacement effect and the structure of the compounds are discussed.In conclusion, we thank A. A. Trushanov for help in conducting the experiments.     

Dynamics of positron scattering from lithium,sodium and potassium atoms in hot and dense plasmas

The dynamics of positron scattering from the ground state of lithium, sodium and potassium atoms in hot and dense plasmas has been investigated by applying a two-state approximation that includes elastic scattering and rearrangement scattering. The wave functions and energies of the target alkali atoms have been determined quite accurately within the framework of the ’method of model potential’. An inclusive study was made on the effects of plasma screening on the differential and total cross sections for elastic scattering and positronium formation in the ground state for the incident positron energy lying within 10 eV to 500 eV. For the unscreened case, our present results agree reasonably with the results of other calculations. It was found that the cross sections suffer considerable change due to the effects of the background plasma.     

Theoretical studies on the structure,sensitivity, density,thermodynamic properties and detonation performance of dinitrobitriazoles

Azodinitro- and dinitroethylene-bridged bitriazoles are of interest in the contest of high explosives, and were found to have true local energy minima at the B3LYP/aug-cc-pVDZ level of theory. The optimised structures, vibrational frequencies and thermodynamic quantities for bitriazoles were obtained in the ground state. Kamlet–Jacobs equations were used to evaluate the performance of bitriazoles based on the predicted density and the calculated heat of explosion. Detonation properties (D = 8.12 to 9.23 km s^?1 and P = 28.0 to 39.83 GPa) of bitriazoles were found to be promising compared with those of hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX, D = 8.75 km s^?1 and P = 34.7 GPa) and octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX, D = 8.96 km s^?1 and P = 35.96 GPa). The fusion of azoles particularly appears to be a promising area for investigation, since it may lead to the desirable consequences of higher heat of explosion, higher density and thus improved detonation performance.     

Photorefractive properties of potassium lithium niobate doped with copper

Potassium lithium niobate doped with copper (Cu:KLN) were grown by the Czochralski method for the first time. The structure of Cu:KLN was measured by the x-ray powder diffraction method, and its lattice constants were obtained. The position of copper ions in KLN crystal was determined. The exponential gain coefficient, response time and erasure time were measured. It was found that the exponential gain coefficient of Cu:KLN is 10.5 cm⁻¹, as two times high as that of KLN, and its response time of 1.53 s is one order of magnitude shorter than that of Cu:LiNbO₃. The type of light exciting carriers in Cu:KLN has been investigated. The result showed that the electron acts the main role in Cu:KLN.     

Theoretical analysis of structure, thermodynamic properties, and optical properties of Ge-doped amorphous SiO2

Different stable geometric configurations of Ge doped amorphous SiO₂ (a-SiO₂) system, originating from one, two, or three Si atoms in various places of the a-SiO₂ substituted by Ge atoms randomly have been investigated using interatomic potentials in this work. The most stable structures have been identified and corresponding evolutional rules obtained. The structural growth pattern for Ge-doped a-SiO₂ system is that Ge atoms tend to spread far away from each other and keep away from the center. Furthermore, the thermodynamic properties including speci?c heat, Debye temperature, vibrational entropy, and so on are calculated from the structure with 16 Si atoms of the constructed a-SiO₂ cell replaced by Ge atoms and with the biggest Ge-Ge distance. It can be seen that entropy of Ge doped system with larger specific heat is higher than that of the pure system with smaller specific heat. At last, optical properties including optical absorption spectrum and electron energy loss function of nGe-doped a-SiO₂ (n=0-3, 8) system is also obtained.     

2,5-二(4-溴甲基苯基)-1,3,4噁二唑分子的结构、光谱与热力学性质的理论研究

采用密度泛函理论在B3LYP/6-31+G*水平计算研究2,5-二(4-溴甲基苯基)-1,3,4噁二唑分子的结构、光谱、热力学性质.结果显示,优化得到的最稳定结构的三个环同在一个平面,两个溴原子偏离平面120°,分别位于平面两端正反方向.气相中最强吸收峰出现在315 nm,为S0到S1的电子跃迁,溶剂作用使其红移4～6 nm.热力学计算表明,标准摩尔焓、标准摩尔热容和标准摩尔熵分别与温度存在二次函数关系.298.15 K,2,5-二(4-溴甲基苯基)-1,3,4噁二唑分子的标准摩尔生成焓和标准摩尔生成自由能分别为2708.95和2972.13kJ.mol-1.