高温高压下闪锌矿相GaN结构和热力学特性的分子动力学研究

利用分子动力学方法和Buckingham经验势模型对重要半导体材料GaN立方闪锌矿相的晶格常数、相变压力(从闪锌矿到岩盐结构)、热膨胀、等温体模量、定压热容等结构和热力学特性在300—3000K的温度范围和0—65GPa的压力范围内进行了研究.研究表明，闪锌矿相GaN常态下的结构和热力学参数的模拟结果与实验数据及其他理论结果相符.同时在所选作用势模型可靠性检验的基础上，对等温体模量、定压热容诸非谐性参量在高温高压下的热力学行为进行了预测.所得结果在材料科学等领域的研究中具有一定的应用背景和参考价值. 关键词： GaN Buckingham势 分子动力学模拟 高温高压     

闪锌矿相GaN热容和格林爱森参数

利用壳层模型分子动力学方法，在高温高压条件下对闪锌矿相GaN的压力体积关系、定压和定容热容及格林爱森参数进行了比较研究，其中Ga-Ga、Ga-N和N-N三组离子对间的相互作用通过极化势模型来描述，即出于对半导体材料GaN离子特性的考虑而分别给予Ga离子和N离子以两组不同大小的电荷．结果表明计算得到的环境条件下的热力学参数和最近的其他理论结果吻合，同第一性原理计算结果比较，定容热容在低温下的差别可以用来解释不同方法所采用的不同近似机制．最后在300?2000 K和0?40 GPa条件下，对闪锌矿相GaN的物理特性做了总结．     

氟化镁高压萤石结构稳定性及热物性的数值模拟

氟化镁(Mg F2)是工业用途广泛的重要碱土金属氟化物,也是矿物质氟镁石的主要成分,相比于电子结构和光学特性的研究,人们从地球物理学的角度给予Mg F2高压热物性的研究明显不够,而组成地球下地幔矿物的高压熔化、热膨胀等热物性预测对理解地球的结构、动力学、演化及起源至关重要.本文利用基于密度泛函理论的第一性原理方法,通过热力学、动力学、力学稳定性计算表明萤石结构为Mg F2高压结构,根据等焓原理,分别结合广义梯度近似和局域密度近似确定出了零温下Mg F2晶体从稳定金红石结构到高压萤石结构的相转变压力为19.26 GPa和18.15 GPa,且萤石结构至少稳定到135 GPa (相当于下地幔压力);利用基于有效势参数模型的经典分子动力学方法,通过模拟特定压力下Mg F2体系的摩尔体积、总能随温度的变化确认了Mg F2萤石结构在300—6000 K温度范围内的高温稳定性.在此基础上,考虑选用能够提高密堆固体平衡特性的交换相关泛函形式的广义梯度近似方法且结合准谐德拜模型,以及利用根据从头算HartreeFock方法获得的数据拟合得到的可靠经验势参数结合经典分子动力学方法,共同预测了萤石结构的Mg F2在300—1500 K和0—135 GPa的温度和压力范围内的体积热膨胀系数、等温体模量、热弹性参数等重要热力学参量.研究表明:Mg F2萤石结构基于体积热膨胀系数和等温体模量得到的热弹性参数并非物态方程研究中通常假定的常数,但在高温高压条件下,其值接近于常数.     

高压下CaPo弹性性质和热力学性质的第一性原理研究

利用密度泛函理论的平面波赝势方法预测研究了CaPo从岩盐结构(B1结构)到氯化铯结构(B2结构)的相变以及B1结构CaPo高压下的弹性性质以及热力学性质等.通过等焓原理发现B1→B2的相变压力为22.8GPa. 同时计算了B1结构CaPo高压下的弹性常数以及剪切模量、杨氏模量等相关弹性参数,结果发现当压力超过20GPa时,B1结构CaPo开始不稳定了,这和等焓原理所得结果相符合. 最后通过Debye模型成功获取了B1结构C 关键词： 相变 弹性性质 热力学性质 CaPo     

下地幔条件下钙钛矿结构MgSiO3熔化行为的研究

利用分子动力学方法结合有效的对势,模拟了下地幔条件下钙钛矿结构MgSiO3的熔化曲线．研究表明,分子动力学模拟结果精确地再现了广泛压强范围内钙钛矿结构MgSiO3的状态方程,并且熔化曲线与最新的实验结果也符合的很好．在压强上升到下地幔压强范围内,压强低于60 GPa时的钙钛矿结构MgSiO3熔化曲线比较陡,接着变得平缓．在核幔边界压强135 GPa时,钙钛矿结构MgSiO3的熔化温度是6500 K,明显低于Zerr和Boehler实验结果的外推结果．     

ZnSe高压相变和声子谱的第一性原理研究

采用基于第一性原理的平面波赝势和广义梯度近似方法,对闪锌矿(ZB)、纤锌矿(WZ)和岩盐(RS)结构的ZnSe在0~40GPa压力下的热力学性质及相变特性进行了研究。通过数值计算得出3种结构ZnSe的能量随体积变化的曲线,在此基础上,研究了不同结构ZnSe的晶格常数、高温高压物态方程、结构相变及弹性性质,解释了高压下结构相变的机理,并通过焓相等原理得到ZB结构到RS结构的相变压力为14.95GPa。最后,利用VASP软件结合Phonopy计算了ZB结构和RS结构ZnSe的声子谱,并将温度效应引入,得到亥姆霍兹自由能、熵和等容热容随温度的变化关系。     

高压下钙钛矿结构MgSiO3的分子动力学研究

利用分子动力学方法,研究了高温高压下钙钛矿结构MgSiO3的状态方程.研究表明,分子动力学模拟结果很好地再现了广泛温度和压强范围内钙钛矿结构MgSiO3的摩尔体积.温度300 K压强上升到120 GPa模拟的钙钛矿结构MgSiO3状态方程和有效的实验结果基本一致.在更高温度和更高压强下模拟的钙钛矿结构MgSiO3状态方程和他人的计算值吻合的很好.另外,还分别计算了温度300 K,900 K,1500 K和2500 K压强上升到120 GPa时MgSiO3的体积压缩率.     

多形性相变的分子动力学模拟

 本文利用分子动力学方法研究了KCl晶体在ρ＝ρ₀时的温度相变。面心立方（fcc）和体心立方（bcc）两种结构的径向分布函数随温度的变化的情况说明，在高压下，发生着bcc结构相fcc结构的转变，bcc结构是不稳定的。为了选取合理的势参数，利用了分子动力学程序在T＝0时的性质，计算了NaCl和KCl晶体的零温状态方程，研究了它们在压力作用下发生的多形性相变。计算表明，NaCl和KCl晶体将分别于18.8 GPa和5.9 GPa发生从fcc到bcc的多形性相变，这些值相当接近实验结果。着说明本文选用的势参数势有一定精度的。     

高压下液态硝基甲烷的分子动力学模拟

 对高压下液态硝基甲烷的性质进行经典和基于第一性原理计算的Car-Parrinello分子动力学（CPMD）模拟。利用经典势的分子动力学（MD）模拟研究了高压压缩状态下液态硝基甲烷的结构和热力学性质,得到了高达14.2 GPa压力下的理论Hugoniot数据。对于一些热力学函数,如总能和粒子速度,经典势模拟给出了很好的总趋势,基本特征和实验观测一致。但是在给定的密度下,经典模拟预言的Hugoniot压力偏高。在几个选定的密度下,进行了CPMD模拟,得到了二体相关函数、速度自相关函数、振动光谱和其它的热力学性质,并与经典模拟结果进行了比较。对二体相关函数的分析表明经典势的短程部分的刚性可能太强,从而导致了比实验值高的理论压力值。对于某些二体相关函数,CPMD模拟和经典模拟结果差别很大,可以归结为量子效应。当压力增高时,量子模拟得到的振动光谱向高频部分移动的现象与实验观测相符合。     

高压下MgO的热弹性研究

利用第一原理平面波赝势方法和广义梯度近似研究了广泛温度和压强范围内MgO的热弹性特性．MgO从低压NaCl到高压CsCl结构的相变压强为397 GPa，表明它在地球内部不会发生相变．在压强上升到150 GPa时，MgO的绝热弹性模量跟0 GPa时的实验值和其他赝势在高压下的计算结果基本一致．从0 GPa上升到20 GPa时，MgO的各向异性逐渐减小；在20?150 GPa时绝对值逐渐增大．MgO明显地违背了Cauchy条件，反应出非中心多体力是重要的．另外，MgO的热力学参量与实验也符合的很好．     

Thermal expansivity and bulk modulus of ZnO with NaCl-type cubic structure at high pressures and temperatures

The thermal expansivity and bulk modulus of ZnO with NaCl-type cubic structure were estimated by using the constant temperature and pressure molecular dynamics technique with effective pair potentials which consist of the Coulomb, dispersion, and repulsion interaction at high pressures and temperatures. It is shown that the calculated thermodynamic parameters including linear thermal expansion coefficient, isothermal bulk modulus and its pressure derivative are in good agreement with the available experimental data and the latest theoretical results. At an extended pressure and temperature ranges, linear thermal expansion coefficient and isothermal bulk modus have also been predicted. The thermodynamic properties of ZnO with NaCl-type cubic structure are summarized in the pressure 0–150 GPa ranges and the temperature up to 3000 K.     

Melting and isothermal bulk modulus of the rocksalt phase of ZnO with molecular dynamics simulation

The Buckingham potential has been employed to simulate the melting of the rocksalt phase of ZnO over a wide pressure–temperature range and isothermal bulk modulus with shell model molecular dynamics method. The melting curve from molecular dynamics simulations is in good agreement with the results obtained from Lindemann melting equation in the pressure below 7 GPa. The calculated null compression bulk modulus is compared with the available experimental data and other theoretical results. At extended temperature ranges, the isothermal bulk modulus has also been predicted up to 3000 K.     

Molecular dynamics simulation of P-V-T relationship of ZnO with rock-salt structure using pair-wise interactions

Molecular dynamics (MD) method is used to investigate the behavior of the pressure-volume-temperature (P-V-T) relationship, lattice constant and thermal expansivity for ZnO with rock-salt structure at high pressures and temperatures. The interionic potential is taken to be the sum of pair-wise additive Coulomb, van der Waals attraction, and repulsive interactions. The isothermal and isobaric properties are discussed from the corresponding P-V-T relationship, and it is shown that the MD simulation is successful in reproducing the measured volumes of ZnO over a wide range of temperature and pressure. Meanwhile, the equations of state parameters including lattice constant, linear thermal expansion coefficient, and isothermal bulk modulus are calculated and compared with the available experimental data and the latest theoretical results. At an extended pressure and temperature range, P-V-T relationship, lattice constant, and linear thermal expansion coefficient have been predicted. The structural and thermodynamic properties of ZnO with rock-salt structure are summarized in the pressure 0-100 GPa ranges and the temperature up to 3100 K.     

高压下碱卤晶体的三参量等温状态方程

 由等温体积弹性模量的定义及其与压强关系的假设出发，导出了一个新的适用于高压下碱卤晶体的三参量等温状态方程。计算了室温下NaCl晶体在0～30 GPa压强范围内、CsCl晶体在0～40 GPa压强范围内的相对体积以及NaCl晶体在0～30 GPa压强范围内的等温体积弹性模量，计算结果与实验值一致。对等温体积弹性模量及其对压强的一阶、二阶导数与压强的关系进行了讨论，指出压强趋于无穷大时的等温体积弹性模量是常数。     

Simulated equation of state of CaF2 with fluorite-type structure at high temperature and high pressure

The pressure-volume-temperature (P-V-T) equation of state (EOS), isothermal bulk modulus, and thermal expansivity of CaF₂ with cubic fluorite-type structure are investigated using the constant temperature and pressure shell model molecular dynamics (MD) method with effective pair potentials which consist of the Coulomb, dispersion, and repulsion interaction. It was shown that MD simulation is very successful in accurately reproducing the measured volumes of the CaF₂ over a wide range of pressures. The simulated P-V data matched X-ray diffraction experimental results up to 9.5 GPa at 300 K. In addition, volume thermal-expansion coefficient and isothermal bulk modulus were also calculated and compared with available experimental data and the latest theoretical results at ambient condition. At extended temperature and pressure ranges, The P-V EOS under different isotherms at selected temperatures, T-V EOS under different isobars at selected pressures, thermal expansivity, and isothermal bulk modulus were predicted up to 1500 K and 10 GPa. The detailed knowledge of thermodynamic behavior and EOS at extreme conditions are of fundamental importance to the understanding of the physical properties of CaF₂.     

Isothermal bulk modulus and its first pressure derivative of NaCl at high pressure and high temperature

The isothermal bulk modulus and its first pressure derivative of NaCl are investigated using the classical molecular dynamics method and the quasi-harmonic Debye model.To ensure faithful molecular dynamics simulations,two types of potentials,the shell-model(SM) potential and the two-body rigid-ion Born-Mayer-Huggins-Fumi-Tosi(BMHFT) potential,are fully tested.Compared with the SM potential based simulation,the molecular dynamics simulation with the BMHFT potential is very successful in reproducing accurately the measured bulk modulus of NaCl.Particular attention is paid to the prediction of the isothermal bulk modulus and its first pressure derivative using the reliable potential and to the comparison of the SM and the BMHFT potentials based molecular dynamics simulations with the quasi-harmonic Debye model.The properties of NaCl in the pressure range of 0-30 GPa at temperatures up to the melting temperature of 1050 K are investigated.     

Isothermal bulk modulus and its first pressure derivative of NaCl at high pressure and high temperature

The isothermal bulk modulus and its first pressure derivative of NaCl are investigated using the classical molecular dynamics method and the quasi-harmonic Debye model. To ensure faithful molecular dynamics simulations, two types of potentials, the shell-model (SM) potential and the two-body rigid-ion Born-Mayer-Huggins-Fumi-Tosi (BMHFT) potential, are fully tested. Compared with the SM potential based simulation, the molecular dynamics simulation with the BMHFT potential is very successful in reproducing accurately the measured bulk modulus of NaCl. Particular attention is paid to the prediction of the isothermal bulk modulus and its first pressure derivative using the reliable potential and to the comparison of the SM and the BMHFT potentials based molecular dynamics simulations with the quasi-harmonic Debye model. The properties of NaCl in the pressure range of 0-30 GPa at temperatures up to the melting temperature of 1050 K are investigated.     

钝感高能炸药三氨基三硝基苯高温高压下热力学性质的分子动力学模拟研究

热力学性质是钝感高能炸药1, 3, 5-三氨基-2, 4, 6-三硝基苯(TATB)爆轰性质和安全性评估分析的重要参数. 由于结构的复杂性, TATB炸药尚缺乏系统的实验和理论计算结果. 结合全原子力场和分子动力学的方法, 本文系统研究了不同温度和压力条件下TATB的力学性质和热力学参数, 得到了弹性模量、德拜温度等随温度、压力的变化情况, 并与实验进行了对比分析. 结果表明: 在 0-50 GPa外部压力下, TATB晶体保持力学稳定, 弹性常数和弹性模量随压力升高而增大, 各向异性程度随压力升高而减小, 泊松比和延展性则受压力的影响较小; 随温度的升高, TATB的力学稳定性逐渐下降, 有发生力学失稳的可能, 各弹性常数随温度升高而逐渐减小, 各向异性程度也随之减小; TATB 的声速和德拜温度同样随着压力升高而增大, 平均声速从0 GPa下的1833 m/s, 增加到10 GPa 下的3143 m/s, 德拜温度由0 GPa下的254 K增加到10 GPa的587 K. TATB 热膨胀系数的计算表明, 在200-500 K 温度常压情况下, 其体热膨胀系数为35.9×10^-5 K^-1, 与实验数据符合较好.     

Elastic,Piezoelectric and Acoustic Properties of Wurtzite MnO from Density Functional Calculation

The wurtzite MnO has been obtained lately and is expected to have large potential in varies applications.Since elastic properties are the bases of various applications, we calculate these properties of wurtzite MnO based on the density-functional theory and compare it with other two phases of MnO (rocksalt and zinc-blende MnO). The Young's modulus of wurtzite and zinc-blende MnO are 65.6 GPa and 73.4 GPa, respectively, which are much lower than those of rocksalt MnO (177.6 GPa). More importantly, both the Poisson ratio and the bulk modulus to shear modulus ratio indicate that wurtzite MnO should have much better ductile properties than rocksalt MnO. The calculated piezoelectric constants of wurtzite MnO are comparable to those of ZnO. This suggests wurtzite MnO is a good piezoelectric material.Furthermore, the slowness surfaces of acoustic waves of them are given from Christoffel equation.