单次冲击压缩下液态硝基甲烷的拉曼光谱

在单次冲击压缩实验中,运用高敏度瞬态拉曼光谱技术观测了液态硝基甲烷分子的拉曼光谱. 将该拉曼测量技术与二级轻气炮的实验平台结合起来,获得硝基甲烷分子振动模式的高压动态行为. 硝基甲烷被12 GPa压力冲击时的拉曼光谱可清晰探测,其拉曼振动峰仅仅发生了峰位蓝移和峰宽展宽的变化,未显示出化学变化产生的迹象.     

液态硝基甲烷热分解行为及压力效应的第一性原理研究

采用基于密度泛函理论的第一性原理分子动力学方法对液态硝基甲烷的热分解行为进行了模拟,结合各产物布居数随时间的演化,讨论了热分解初期可能发生的3种反应,即分子内/分子间的质子迁移反应和C—N键的断裂.在长时间（30 ps）的模拟过程中,H₂O是主要产物.研究了液态硝基甲烷在不同密度（压力）条件下热分解的动力学行为.发现不同密度（压力）条件下液态硝基甲烷热分解呈现明显不同的变化趋势,并给出了解释. 关键词： 硝基甲烷 分子动力学 热分解 压力效应     

液氩多体作用势研究及其Hugoniot曲线的分子动力学模拟

应用Hartree－Fock方法,计算了氩体系的多体相互作用.对Parson等提出的MSVⅢ势进行了 多体修正,并将修正后的MSVⅢ势用于液氩物态方程的分子动力学模拟.计算表明,修正后 的MSVⅢ势能较好地反映液氩在所研究压力范围的情况,计算的Hugoniot曲线与实验结果在 冲击压力高达40?GPa密度区的符合程度得到改善.     

冲击高压下硝基甲烷的拉曼光谱及其结构稳定性

在单次冲击压缩实验中,借助新建的瞬态拉曼光谱技术实现了对液态硝基甲烷冲击拉曼光谱的原位观测,来探究该样品分子在冲击波作用下的结构稳定性。实验发现,在10.6GPa的冲击加载下硝基甲烷的拉曼特征峰仅发生了蓝移和展宽,而在观测波段未发现化学变化产生的迹象。这一结果否定了文献所报道的硝基甲烷在6GPa~8.5GPa的单次冲击压力区间内发生了化学反应的推论,同时也证实了在10.6GPa的冲击压力下硝基甲烷分子在约为516ns的压缩时间内能够保持其结构的稳定。     

冲击高压下硝基甲烷的拉曼光谱及其结构稳定性

在单次冲击压缩实验中,借助新建的瞬态拉曼光谱技术实现了对液态硝基甲烷冲击拉曼光谱的原位观测,来探究该样品分子在冲击波作用下的结构稳定性.实验发现,在10.6 GPa的冲击加载下硝基甲烷的拉曼特征峰仅发生了蓝移和展宽,而在观测波段未发现化学变化产生的迹象.这一结果否定了文献所报道的硝基甲烷在6 GPa~8.5 GPa的单次冲击压力区间内发生了化学反应的推论,同时也证实了在10.6GPa的冲击压力下硝基甲烷分子在约为516 ns的压缩时间内能够保持其结构的稳定.     

硝基甲烷振动能量弛豫的集体模型

用分子动力学方法结合Dlott等人提出的"门槛模"理论研究集体相互作用下硝基甲烷振动能量弛豫过程.其中振动冷却过程与实验符合的很好.在振动激发过程的分子动力学模拟中观测到与实验一致的基频频移现象.用分子动力学方法从微观上详细地描述出分子"门槛模"振动激发过程.研究表明,在高温高压作用下,集体作用效应对多原子振动激发具有不可忽视的作用,能量传递过程中除了基频的作用外,强烈的非线性相互作用引起的振动模泛频也携带有大量的振动能,这些泛频也对分子振动能量传递产生重要影响.     

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     

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     

Ni50Al50合金的液固转变及晶体生长过程的分子动力学模拟

采用分子动力学模拟技术研究了液态Ni50Al50合金在不同 冷速下的凝固特点,模拟采用EAM作用势,计算了不同温度,不同冷速下Ni50Al5 0的偶分布函数。结果表明EAM作用势能很好地描述液态Ni50Al50的无序结构 ,在快速凝固条件下,液态Ni50Al50形成非晶,当冷速较慢时,液态Ni50 Al50形成晶体,分析了不同冷速下体系的相变热力学及相变动力学特点。最后采 用液固两层构型法,清楚地观察到Ni50Al50晶体生长的全过程。     

Ni_(50)Al_(50)合金的液固转变及晶体生长过程的分子动力学模拟

采用分子动力学模拟技术研究了液态Ni50 Al50 合金在不同冷速下的凝固特点 ,模拟采用EAM作用势 ,计算了不同温度 ,不同冷速下Ni50 Al50 的偶分布函数。结果表明EAM作用势能很好地描述液态Ni50 Al50 的无序结构 ,在快速凝固条件下 ,液态Ni50 Al50 形成非晶 ,当冷速较慢时 ,液态Ni50 Al50 形成晶体 ,分析了不同冷速下体系的相变热力学及相变动力学特点。最后采用液固两层构型法 ,清楚地观察到Ni50 Al50 晶体生长的全过程。     

Modeling hot, dense hydrogen with a classical spin dependent hamiltonian

Hot, dense hydrogen is studied with a classical model in which the interaction energy between atoms depends on their internal spins as well as their separation distance. The spins are treated as classical variables. This model is used in Monte Carlo simulations to calculate internal energies, pressures, and pair correlation functions, as well as the Hugoniot for shocked liquid deuterium. The results clearly show the transition of hot, dense hydrogen from a molecular to an atomic fluid. Our results are in reasonable agreement with far more elaborate quantum mechanical simulations.     

Molecular Dynamics Simulations of the Elastic Anisotropy of Pd at Extreme Conditions

It is very interesting to discover the elastic properties of engineering material palladium, especially its elastic anisotropy along Hugoniot states. We here investigate the evolution of its high pressure and temperature(PT) elastic ansotropy along Hugoniot using molecular dynamics simulations based on accurate classical interatomic potential. In order to testify the validity of the interatomic potential of Pd in describing the high PT elastic properties, we calculate its isothermal and adiabatic elastic moduli using molecular dynamics method. The obtained data are in good agreement with experimental data. From the isothermal elastic constants, we deduce the Hugoniot acoustic velocities and find that the resulting data are in good agreement with experimental acoustic velocity data. Based on the reliable elastic constants, we further investigate the spacial elastic ansotropy along Hugoniot PT states. It is found that the spacial elastic anisotropy of Pd increases along Hugoniot states.     

Molecular dynamics simulation of HCl in liquid Ar

Molecular dynamics simulations of one HCl molecule in liquid Ar at three different thermodynamic states have been carried out. The dynamic properties of both the solute molecule and solvent atoms are discussed. Results for Ar in the first solvation shell of HCl are compared with those for atoms in the bulk. The study includes radial distribution functions, residence times, velocity autocorrelation functions, spectral densities, self - diffusion coefficients, reorientational time correlation functions and infrared spectra.     

Molecular dynamics computation of clusters in liquid Fe–Al alloy

By means of constant pressure molecular dynamics (MD) simulation technique, a series of simulations of the Fe₅₀Al₅₀ alloy have been carried out. The atoms interact via semi-empirical n-body noncentral potential. The pair correlation functions and the pair analysis technique is applied to reveal the cluster evolution in the process of quick solidification. By using the bond orientation order parameters, we have measured both local and extended orientation symmetries for computer-generated models of dense liquid and glass. A lot of polyhedra in liquid system, for example, icosahedra, are also obtained. In order to test the reliance of the computation results, corresponding X-ray diffraction experiments have been performed on the material.     

Molecular Dynamics Simulations of Warm Dense Carbon

We present classical and DFT‐based molecular dynamics (MD) simulations of carbon in the warm dense matter regime (? = 3.7 g/cc, 0.86 eV < T < 8.62 eV [T < 100 eV for classical MD]). Two different classical interatomic potentials are used: 1. LCBOP, designed to simulate condensed (e.g. solid) phases of C, and 2. linearly screened Coulomb (Yukawa) potentials. It is shown that LCBOP over‐predicts minima and maxima in the pair correlation functions of liquid‐C in this regime when compared to the DFT‐MD results. The screened Coulomb model, while under‐correlating at low‐T, seems to produce the correct qualitative features in the static ionic pair distributions at the highest‐T. However, both approaches predict the decay in the ionic contribution of the specific heat as T → ∞ to be much slower than that predicted by a model based on DFT‐MD. These differences in the MD‐derived equations of state in warm dense regimes could have important consequences when using classical inter‐ionic forces such as these in large‐scale MD simulations aimed at studying, for instance, processes of relevance to inertial confinement fusion when C is used as an ablator material. (© 2015 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Structural transition of sheared-liquid metal in quenching state

In this Letter, the effects of shear rate on structural properties of liquid Al in quenching process were investigated via molecular dynamics (MD) simulations based on the EAM potential. Analyses in internal energy and pair correlation functions (PCF) reveal an increasing structural transition temperature as the shear rate is enhanced in the liquid. Results of pair analysis indicate that for liquid Al under normal condition, face center cubic (FCC) structure is clearly detected upon cooling; while in sheared liquid, structural transition from FCC to body center cubic (BCC) at temperature of 800 K is manifested, leading to the dominance of BCC structural order at low temperatures.     

Two-dimensional Yukawa liquids: correlation and dynamics

A combined theoretical and molecular dynamics (MD) simulation study of the collective modes and their dispersion in a two-dimensional Yukawa system in the strongly coupled liquid state is presented. The theoretical analysis relies upon the quasilocalized charge approximation; the MD simulation generates static pair correlation functions and dynamical current-current correlation spectra.     

Experimental and theoretical study of the far-infrared spectra of HCl dissolved in liquid Ar,Kr, and Xe

New experimental results are reported on the relative absorption intensity distribution in the FIR spectra of HCl dissolved in liquefied Ar, Kr, and Xe at several temperatures along the liquid—vapour coexistence curve. These are treated further by applying a previously developed quantum-statistical spectral theory, which accounts for the line mixing and memory effects. Theoretical spectra are given in terms of the anisotropic potential time autocorrelation functions obtained from classical MD simulations using several empirical analytical potentials with density-adjusted well depths. Globally fair agreement between the theoretical and experimental spectra is demonstrated, except in the high frequency wings, where the theory underestimates the observed intensities. The choice of a particular radial form for the anisotropic HCl/RG potentials is found to be not critical for reproducing the experimental absorption profiles.     

Classical Representation of a Quantum System at Equilibrium

A quantum system at equilibrium is represented by a corresponding classical system, chosen to reproduce the thermodynamic and structural properties. The objective is to develop a means for exploiting strong coupling classical methods (e.g., MD, integral equations, DFT) to describe quantum systems. The classical system has an effective temperature, local chemical potential, and pair interaction that are defined by requiring equivalence of the grand potential and its functional derivatives with respect to the external and pair potentials for the classical and quantum systems. Practical inversion of this mapping for the classical properties is effected via the hypernetted chain approximation, leading to representations as functionals of the quantum pair correlation function. As an illustration, the parameters of the classical system are determined approximately such that ideal gas and weak coupling RPA limits are preserved (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Structure,thermodynamic and transport properties of imidazolium-based bis(trifluoromethylsulfonyl)imide ionic liquids from molecular dynamics simulations

Molecular dynamics (MD) simulations have been performed in order to investigate the properties of [C _n mim⁺][Tf₂N^?] (n?=?4,?8,?12) ionic liquids (ILs) in a wide temperature range (298.15?498.15?K) and at atmospheric pressure (1 bar). A previously developed methodology for the calculation of the charge distribution that incorporates ab initio quantum mechanical calculations based on density functional theory (DFT) was used to calculate the partial charges for the classical molecular simulations. The wide range of time scales that characterize the segmental dynamics of these ILs, especially at low temperatures, required very long MD simulations, on the order of several tens of nanoseconds, to calculate the thermodynamic (density, thermal expansion, isothermal compressibility), structural (radial distribution functions between the centers of mass of ions and between individual sites, radial-angular distribution functions) and dynamic (relaxation times of the reorientation of the bonds and the torsion angles, self-diffusion coefficients, shear viscosity) properties. The influence of the temperature and the cation's alkyl chain length on the above-mentioned properties was thoroughly investigated. The calculated thermodynamic (primary and derivative) and structural properties are in good agreement with the experimental data, while the extremely sluggish dynamics of the ILs under study renders the calculation of their transport properties a very complicated and challenging task, especially at low temperatures.