高温高密度条件下氮分子三体关联效应与冲击压缩特性

 基于量子化学从头计算方法,计算了处于高密度条件下氮分子之间的两体排斥势和三体关联势,并采用球面平均近似求得了它们各自的高温平均势能值,得到了包括三体关联效应的等效两体势函数与分子间距的解析关系。借助分子流体微扰变分理论,并考虑van der Waals长程作用,分别采用总平均两体势和总等效两体势,计算了液氮的冲击压缩曲线。计算结果表明,在不需要考虑分子离解的压缩范围内（1～35 GPa）,三体关联效应的贡献使分子间总等效两体势函数比单独两个分子间总平均作用势函数明显软化,与实验Hugoniot数据结果一致。     

液态甲烷的高温密度物态方程理论研究

 采用热力学统计理论研究了液态甲烷在高温高压下分子分解反应特点及该体系的物态方程。着重讨论了体系中CH₄-H₂分子间有效势对体系化学反应平衡及物态方程的影响,并根据实验Hugoniot点(p_H, V)优化确定出其exp-6势函数中的参数值。该势函数的排斥部分值比理想混合条件下Lorentz-Berthelot规则给出的势函数值低约50%,预示着高压下CH₄和H₂之间存在着某种亲合性。用该势函数计算得到的p-T线与现有的两个实验点符合很好。还讨论了CH₄-H₂之间的有效作用势参数对CH₄分子冲击离解度（x）的影响。     

Murrell-Sorbie势下He-HCl碰撞体系微分散射截面的研究

根据在CCSD(T)/aug-cc-pVQZ理论水平下计算的He-HCl相互作用能数据,作者采用Murrell-Sorbie势函数形式拟合了He原子与HCl分子相互作用的各向异性势,并与其它势模型进行了比较;然后采用公认的精确度较高的CC近似方法计算了He-HCl碰撞体系的微分散射截面,总结了非弹性微分散射截面的变化规律.研究表明:采用拟合的各向异性势计算的微分散射截面与实验结果符合得很好.拟合势不但表达形式简洁,而且较好地描述了He-HCl系统相互作用的各向异性特征;利用碰撞体系分子间势的量子化学从头计算结果,可解决势能参数难以确定的问题.对进一步研究原子与分子相互作用的机制有一定的参考价值.     

He-HCl体系各向异性势及分波散射截面的理论研究

首先用BFW势函数形式拟合了在CCSD(T)/aug-cc-pVQZ理论水平下计算的He-HCl相互作用能数据，获得了He原子与HCl分子相互作用的各向异性势；然后采用CC近似方法计算了He-HCl碰撞体系的微分散射截面和分波散射截面，并总结了分波散射截面的变化规律.结果表明，拟合势不但表达形式简洁，而且较好地描述了He-HCl系统相互作用的各向异性特征；利用碰撞体系分子间势的量子化学从头计算结果，可解决势能参数难以确定的问题.对进一步研究原子与分子碰撞机理有一定参考价值. 关键词： 各向异性势 势能参数 密耦近似 分波散射截面     

CO2-CO分子间等效作用势与液态CO冲击压缩特性研究

二氧化碳(CO2)和一氧化碳(CO)是高含碳凝聚态炸药爆轰混合产物中两种重要成分,因此,在研究爆轰反应平衡问题以及爆轰产物状态方程时,必然要涉及到CO2-CO分子间等效作用势的确定问题.本文从反应体系化学平衡的角度,采用分子流体的微扰变分理论(MCR)以及分子混合物的范德瓦耳斯单相流体模型(vdW-1f),对过去和最近发表的液态CO的冲击压缩实验数据进行了详细分析,重新优化了CO2-CO分子间exp-6型势函数中的参数值.讨论了本文确定的CO2-CO分子间等效作用势与过去所采用的势函数之间存在的差别.     

纳米结构泡沫金冲击响应的分子动力学模拟

采用分子动力学计算程序对纳米结构泡沫金(Au)的冲击响应进行了模拟,得到了不同疏松度条件下泡沫Au的冲击压缩特性。通过获取不同势函数条件下实密Au的冲击Hugoniot关系以及泡沫结构稳定性测试选取适合描述Au泡沫冲击过程中原子的相互作用势。采用密堆积球壳的方式建立泡沫Au的初始构型。通过改变空心球壳的尺寸得到不同疏松度的稳定的泡沫Au结构。对泡沫Au的冲击过程进行分子动力学模拟,获得了不同疏松度泡沫Au在不同冲击压缩强度下的热力学状态参数。将模拟结果与已有的状态方程数据库以及疏松物质冲击压缩模型进行比较,结果表明,计算和理论模型给出的结果仍然存在明显的差异性,亟需通过进一步实验研究来验证模拟计算和理论模型结果的可靠性。     

He-NO碰撞体系微分截面的理论计算

首先用Huxley势函数形式拟合了在RCCSD(T)/aug-cc-pVTZ+bf理论水平下计算的He-NO相互作用能数据，获得了He原子与NO分子相互作用的各向异性势，然后采用密耦近似方法计算了He-NO碰撞体系的总微分截面、弹性微分截面和非弹性微分截面，并总结了微分散射截面的变化规律. 结果表明，拟合势不但表达形式简洁，而且较好地描述了He-NO系统相互作用的各向异性特征；利用碰撞体系分子间势的量子化学从头计算结果,可解决势能参数难以确定的问题，对进一步研究原子与分子碰撞机理有一定参考价值. 关键词： 各向异性势 势能参数 密耦近似 微分截面     

He-NO碰撞体系分波截面的理论计算

首先用Huxley势函数拟合在RCCSD(T)/aug-cc-pVTZ bf理论水平下计算的He-NO相互作用能数据,从而得到了He原子与NO分子相互作用各向异性势;然后用密耦近似方法计算了He-NO碰撞体系的总分波截面、弹性分波截面和非弹性分波截面,并总结了分波截面的变化规律.计算结果表明,拟合势较好地描述了He-NO系统相互作用的各向异性特征,利用碰撞体系分子间势的量子化学从头计算结果,可解决势能参数难以确定的问题,对进一步研究原子与分子碰撞机理有一定参考价值.     

He-N2碰撞体系散射截面的理论研究

本文运用量子化学从头计算MP2方法6-311 G(3df,2p)基组,计算了He-N2相互作用的势能,拟合出He原子与N2分子相互作用的各向异性势函数,其势函数参数:势能球平均势阱位置、势阱深度、势能零点位置与通过散射实验数据分析的ESMSV(Exponential-Spline-Morse-Spline-Van der waals)势比较吻合.然后,用公认精确度高的密耦方法计算了He原子与N2分子碰撞体系的总微分截面、弹性微分截面、转动激发的非弹性微分截面和积分截面,计算结果与实验数据符合得较好.     

高温高密度氢(氘)的物态方程——离解效应研究

 高温高压下流体氢将发生离解化学反应,形成具有相互作用的氢分子和氢原子混合体系,此时粒子间的相互作用复杂。利用单组分流体近似的范德瓦尔斯混合模型,将混合物粒子间的相互作用等效为单组分粒子间相互作用,从而简化了对体系的统计热力学处理;并由自由能函数极小化确定化学平衡时各组分含量、体系的内能、压强。研究了温度在10 000 K以下、密度在0.6 g/cm³以下（相应摩尔体积大于3.3 cm³/mol）区间的热致离解和压致离解现象对流体氢（氘）状态方程的影响。所得结果与双组分流体变分理论计算以及第一原理的分子动力学模拟、蒙特卡罗模拟结果以及二级轻气炮实验数据进行了比较,它们之间的一致性表明：用单组分流体近似的范德瓦尔斯混合模型处理氢（氘）分子的离解区域的物态方程是成功的。     

Equation of state and interaction potential of helium under high temperatures and high densities

Based on the thermodynamics statistic method, the improved variational perturbation theory and the modified quantum mechanics correction model have been used to calculate the equation of state of liquid helium at pressure from 0.7 to 108 GPa. The calculation results are in good agreement with the experimental data. The EXP-6 potential (α = 13.1) can more accurately describe the interaction of helium atoms than other potentials in the scheme. Finally, a comparison is shown between our interatomic potentials and other potentials.     

Molecular dynamics study for the melting curve of MgO at high pressure

Shell-model molecular dynamics method is used to study the melting temperatures of MgO at elevated temperatures and high pressures using interaction potentials. Equations of state for MgO simulated by molecular dynamics are in good agreement with available experimental data. The pressure dependence of the melting curve of MgO has been calculated. The surface melting and superheating are considered in the correction of experimental data and the calculated values, respectively. The results of corrections are compared with those of previous work. The corrected melting temperature of MgO is consistent with corrected experimental measurements. The melting temperature of MgO up to 140GPa is calculated.     

Structure and dynamics of liquid formamide at high pressure and high temperature: comparison of X-ray diffraction and molecular dynamics results

New molecular dynamics simulations with optimised potentials for liquid simulation are presented for liquid formamide at high pressures and high temperatures. The structural results are compared to those found by X-ray diffraction measurements, and the H-bonding structure is analysed in detail. While it is ambiguous from purely experimental data, the simulation results support the idea that pressure increase can enhance ring dimer formation at the expense of linear chain structure, but increasing temperature results in an opposite effect. Dynamical results (reorientational correlation times and lifetimes of hydrogen bonds) are in agreement with these findings.     

Structural, electronic and vibrational properties of InN under high pressure

The structural, electronic and vibrational properties of InN under pressures up to 20 GPa have been investigated using the pseudo-potential plane wave method (PP-PW). The generalized-gradient approximation (GGA) in the frame of density functional theory (DFT) approach has been adopted. It is found that the transition from wurtzite (B4) to rocksalt (B1) phase occurs at a pressure of approximately 12.7 GPa. In addition, a change from a direct to an indirect band gap is observed. The mechanism of these changes is discussed. The phonon frequencies and densities of states (DOS) are derived using the linear response approach and density functional perturbation theory (DFPT). The properties of phonons are described by the harmonic approximation method. Our results show that phonons play an important role in the mechanism of phase transition and in the instability of B4 (wurtzite) just before the pressure of transition. At zero pressure our data agree well with recently reported experimental results.     

Thermodynamic properties of MgO under high pressure from first-principles calculations

The equations of state (EOS) and other thermodynamic properties of the rocksalt (RS) structure MgO are investigated by ab initio plane-wave pseudopotential density functional theory method. The obtained results are consistent with the experimental data and those calculated by others. Through the quasi-harmonic Debye model, in which the phononic effects are considered, the dependences of relative volume V/V₀ on pressure P, cell volume V on temperature T, and Debye temperature Θ and specific heat C_V on pressure P are successfully obtained. The variation of the thermal expansion with temperature and pressure is investigated, which shows the temperature has hardly any effect on the thermal expansion at higher pressure.     

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.     

壳层模型分子动力学在CaO研究中的应用

利用壳层分子动力学方法结合有效的对势,研究了高压条件下CaO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CaO的状态方程。研究中考虑了分子动力学模拟熔化存在的过热现象,通过晶体的现代熔化理论,对CaO的分子动力学模拟熔化温度进行了修正,获得了高温高压下CaO正确的熔化温度。因此,常压下引入壳层模型的分子动力学为研究物质熔化提供了一个很好的方法,这种方法可进一步推广到其它物质的高压熔化研究中。     

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.     

Heat capacity of ZnO with cubic structure at high temperatures

The heat capacities at constant pressure and constant volume, and thermal expansivity are calculated for ZnO with rocksalt-type and zinc-blende-type cubic structures over a wide range of temperatures using molecular dynamics simulations with interactions due to effective pair-wise potentials which consist of the Coulomb, dispersion, and repulsion interaction. It is shown that the calculated structural and thermodynamic parameters including lattice constant, thermal-expansion coefficient, isothermal bulk modulus and its pressure derivative at ambient condition are in good agreement with the available experimental data and the latest theoretical results. At extended pressure and temperature ranges, lattice constant and heat capacity have also been predicted. The structural and thermodynamic properties of ZnO with cubic structure are summarized in the 300-1500 K temperature ranges and up to 100 kbar pressure.     

Structural and elastic properties of TiN under high pressure

We have investigated the structural and elastic properties of TiN at high pressures by the first-principles plane wave pseudopotential density functional theory method at applied pressures up to 45.4 GPa. The obtained normalized volume dependence of the resulting pressure is in excellent agreement with the experimental data investigated using synchrotron radial x-ray diffraction (RXRD) under nonhydrostatic compression up to 45.4 GPa in a diamond-anvil cell. Three independent elastic constants at zero pressure and high pressure are calculated. From the obtained elastic constants, the bulk modulus, Young's modulus, shear modulus, acoustic velocity and Debye temperature as a function of the applied pressure are also successfully obtained.