液态N2、CO冲击压缩特性研究

 介绍利用液氮致冷技术实现低温靶的冷却及样品气体的液化,并通过二级轻气炮对液态气体加载进行平面冲击压缩,实验分别测得10～57 GPa一次冲击压缩下液氮和液态CO的Hugoniot关系数据。这些实验数据结果显示,33 GPa以上比其以下更容易压缩,这种现象本质是氮发生离解相变消耗内能的一种表现形势。液态在20 GPa以下表现为一种稳定的压缩过程,而在其以上则伴随有较为复杂的化学反应现象产生。此外,实验研究还发现,20 GPa以下N₂和CO两种分子液体的冲击压缩特性非常相似。     

基于Helmholtz自由能模型的聚乙烯的完全物态方程

基于Helmholtz自由能建立了聚乙烯的完全物态方程,通过该模型计算获得了聚乙烯的150 GPa压力范围内的冲击Hugoniot关系、冲击波温度-压力关系,计算结果与已有实验结果和分子动力学计算结果均符合较好,表明构建的物态方程对描述聚乙烯离解相变压力150 GPa内的热力学量具有很好的适用性.     

高温高密度氩物态方程研究

用Exp-6有效两体势模型和液体变分微扰理论计算了液Ar冲击压缩曲线,在35 GPa以下的压力范围内计算的冲击压缩曲线与Thiel 及Nellis等人的实验数据进行了比较.液体分子间Exp-6有效两体势参数根据实验数据计算优选出最佳值,计算结果表明得到的优选参数较为准确地描述了液Ar分子间相互作用.由理论结合实验数据可以认为液氩体系在冲击压力36 GPa以下无相变现象.对较高冲击压力下理论计算的冲击曲线和实验结果之间的偏差作了分析,结合不透明度实验的结果,得到当压力超过35 GPa,温度在12 000 K     

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。     

(111)轴向锑化铟单晶冲击相变研究

 利用气体炮加载方法研究了(111)轴向锑化铟（InSb）单晶的冲击相变以及剪力对冲击相变的影响。冲击加载应力为1.75~3.80 GPa。实验得到，InSb单晶相变的起始应力由静高压时的2.3 GPa下降到1.727 GPa，最大体积变化率为ΔV/V₀＝15.31%，对应的最大剪力为0.681 GPa，剪力水平为83%左右，相变平均静水压力由静高压时的2.3 GPa，下降到0.823 GPa。研究表明，剪力对锑化铟单晶相变的诱发水平有重大影响。     

稠密流体氮高温高压相变及物态方程

氮的高温高压物态方程以及相图对于研究和制备高能量密度含能材料至关重要.本文采用基于密度泛函理论的分子动力学模拟方法,研究了液氮的高温高压行为,给出900—25000 K, 2—200 GPa区间流体氮的物态方程以及组分、相态变化.在上述相空间,观察到流体氮分子相-聚合物相以及聚合物-原子相的相变发生.获得的液氮Hugoniot理论曲线与实验结果吻合较好,发现30—60 GPa区间Hugoniot曲线的软化与分子-聚合物流体相的相变有关;在60 GPa后Hugoniot曲线变陡峭与流体氮进入聚合物相区有关.     

33 GPa压力以下液氩冲击温度的实验测量

 利用液氮冷靶系统制取液氩样品，以二级氢气炮作为加载工具，驱动飞片对液氩样品进行平面冲击压缩，实验测量了33 GPa冲击压力以下液氩的冲击温度。飞片速度由磁测速系统测量，冲击波速度和冲击温度用光纤耦合高温计系统测量，粒子速度采用阻抗匹配法计算得到。实验测得当冲击压力为33 GPa时，液氩的冲击温度超过10 000 K；而当冲击压力超过30 GPa时，冲击温度的上升趋势与理论计算相比明显变缓，该压力点正好与以前测得的冲击波速度-粒子速度曲线的拐点一致。     

碳水混合物冲击压缩特性的理论研究

 采用固-液双相混合模型和分子流体的微扰变分统计理论,分别计算了石墨-水体系（ρ₀=1.233 g/cm³）和金刚石-水体系（ρ₀=1.238 g/cm³）的冲击压缩特性。结果表明：（1）在不发生石墨→金刚石相变和化学反应的低压区域（p<20 GPa）,这两种混合体系的冲击压缩曲线的差别并不明显;（2）在发生石墨→金刚石相变的高压区域（p>20 GPa）,这两种混合体系的冲击压缩曲线显著不同,且石墨-水体系更易压缩;（3）在45～60 GPa强冲击压力范围内,冲击波诱发的化学反应也不会显著影响这两种体系冲击压缩曲线的走势。上述结论与文献（高压物理学报,1999,13(2):87-92）发表的实验结果相矛盾。进一步分析了引起理论与实验结果不一致的可能原因,并对文献中的实验结果及其理论分析结论提出质疑。     

钒的高压声速测量

采用反向碰撞方法进行了钒冲击实验,利用激光干涉测速技术对V/LiF窗口界面粒子速度剖面进行测量.通过对粒子速度剖面的分析获得了32—88 GPa压力范围内钒的高压声速.实验获得的声速-冲击压力关系在约60 GPa存在间断,表明钒发生了冲击相变.相变压力与静高压实验结果及第一性原理计算结果基本一致.     

用多次冲击压缩方法研究稠密氢氦等摩尔混合气体的物态方程

采用液氮冷却以及气体增压技术，制备了～30MPa及～90K初始状态的氢、氦等摩尔混合气体样品.以二级轻气炮作为加载工具，用不同灵敏度设置的两套多通道瞬态高温计系统获得完整、清晰的稠密氢、氦混合气体多次冲击压缩过程的光谱辐射强度信号.并建立起相应的实验数据处理和分析技术，获得了5—140GPa范围内氢、氦混合气体一至五次冲击雨贡纽物态方程，以及一次、二次和四次冲击温度实验数据.流体变分理论和离解模型用来分析和解释所获得的测量结果. 关键词： 氢、氦混合气体 多次冲击压缩 光谱辐射强度历史 物态方程     

Thermal dissociation of chromium hexacarbonyl and its decomposition products—Unsaturated carbonyls

The thermal dissociation of chromium hexacarbonyl was studied behind incident shock waves by means of molecular and atomic resonance absorption spectroscopies. The results obtained by these two methods were found to be in close agreement with each other and with the published data on the laser pyrolysis of this compound. A joint interpretation of the experimental results on Cr(CO)₆ dissociation obtained in the present work and the available data on the recombination of CO molecules with unsaturated chromium carbonyls, Cr(CO)₅ and Cr(CO)₄, within the framework of the Rice-Ramsperger-Kassel-Marcus theory made it possible to estimate the bond dissociation energies of all six ligands and to determine, for the first time, the corresponding dissociation rate constants in the low- and high-pressure limits.     

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。     

红外聚焦脉冲激光场中同位素浓缩过程的动力学处理

本文从动力学理论出发,导出了在红外聚焦脉冲激光场中分子离解速率和同位素浓缩系数对激光脉冲能量、透镜焦距、激光脉冲辐照次数等参数的关系式。理论公式与SF₆的有关实验结果作了比较,符合得很好。此外,通过理论与实验的比较,提供了进一步研究离解机理的有益信息。 关键词：     

高温高压下爆轰产物分子间相互作用的研究

给出了一种由分子流体的冲击Hugoniot实验数据确定原分子之间和离解产物分子、原子相互间作用势参数的方法. 在较低压强下,采用Ross硬球微扰理论软球修正模型确定原分子之间的相互作用势参数;在较高压强下,采用基于统计物理的化学平衡方法来确定分子离解后的分子和原子之间的相互作用势参数. 与传统的由对应状态定律确定势函数参数的方法相比,所得到的势函数参数在很大的压强范围内都能较好地描述冲击实验. 关键词： 高温高压 化学平衡 冲击Hugoniot实验     

Accurate studies on the full vibrational energy spectra and molecular dissociation energies for some electronic states of N_2 molecule

1 IntroductionAccurate results of high-lying vibrational energies and molecular dissociation energy De of diatomic electronic states are very important for thermodynamics, molecular spec- troscopy, reactive scatterings, and the collision physics of ultracold atoms. For example, the binding energy of the highest bound vibrational state to the ground vibrational state determines the s-wave scattering length. This in turn determines the low- energy (pre- dominantly s-wave) atomic elastic-scatteri…     

H+H2 thermal reaction: a convergence of theory and experiment

New experimental and theoretical rate constants for two isotopologs of the simplest chemical reaction, H+H2-->H2+H, are presented. The theoretical results are obtained using accurate quantum dynamics with a converged Born-Oppenheimer potential energy surface and include non-Born-Oppenheimer corrections. The new experiments are carried out using a shock tube and complement earlier investigations over a very large T range, 167 to 2112 K. Experiment and theory now agree perfectly, within experimental error, bringing this 75-year-old scientific problem to completion.     

Ab initio simulation of phase transitions and dissociation of H2S at high pressure

By ab initio constant pressure molecular dynamics, we have identified the structure of phase V and phase VI of H2S at 35 and 65 GPa, respectively. The theoretical IR spectra of both phases are consistent with experimental findings and support our proposed structural models. We find that phase V is characterized by the presence of charged SH+3 and SH- species which are created and destroyed dynamically, whereas phase VI is no longer a molecular phase but consists of sheets of S with the majority of H intercalated between the layers. The stability of the two phases with respect to dissociation into elemental crystalline hydrogen and sulfur is discussed.     

液氮的冲击压缩理论计算

 使用修正的WCA状态方程研究液氮的冲击压缩特性，并利用exp-6形式的势函数、用Ross变分微扰理论计算分子间相互作用贡献的自由能。计算的液氮冲击压缩Hugoniot曲线与实验数据符合较好。     

Accurate studies on the full vibrational energy spectra and molecular dissociation energies for some electronic states of N<Subscript>2</Subscript> molecule

It is usually very difficult to directly obtain molecular dissociation energy D _e and all accurate high-lying vibrational energies for most diatomic electronic states using modern experimental techniques or quantum theories, and it, is also very difficult to give accurate analytical expression for diatomic molecular dissociation energy. This study proposes a new analytical formula for obtaining accurate molecular dissociation energy based on the LeRoy and Bernstein’s energy expression in dissociation limit. A set of full vibrational energy spectra for some electronic states of N₂ molecule are studied using the algebraic method (AM) suggested recently, and the corresponding accurate molecular dissociation energies are evaluated using the proposed new formula and high-lying AM vibrational energies. The results show that the AM spectra and the new theoretical dissociation energies agree excellently with experimental data, and thereby providing a new physical approach to generating accurate dissociation energies for electronic states of diatomic molecules.     

Accurate studies on the full vibrational energy spectra and molecular dissociation energies for some electronic states of the Li2 molecule

It is usually very difficult to directly obtain molecular dissociation energy D_e and all accurate high-lying vibrational energies for most diatomic electronic states using modern experimental techniques or quantum theories, and it is also very difficult to give accurate analytical expression for diatomic molecular dissociation energy. This study proposes a new analytical formula for obtaining accurate molecular dissociation energy based on the LeRoy and Bernstein's energy expression in dissociation limit. A set of full vibrational energy spectra for some electronic states of Li₂ molecule are studied using the algebraic method (AM) suggested recently, and the corresponding accurate molecular dissociation energies are evaluated using the proposed new formula and high-lying AM vibrational energies. The results show that the AM spectra and the new theoretical dissociation energies agree very well with experimental data, and thereby providing a new physical approach to generating accurate dissociation energies for electronic states of diatomic molecules.