纳米液滴蒸发过程的分子动力学模拟

本文从分子水平对纳米氮液滴蒸发的微观过程进行了分子动力学研究,其中液氮分子间采用球形截断的LJ势能函数.从微观模拟信息中获取了相应的宏观性质,示出了液滴在蒸发过程中的分子位形的变、密度分布、双体分布函数和压力分布,探究了纳米液滴在蒸发过程中界面现象的物理机理.     

LJ流体非牛顿现象的分子动力学模拟

使用非平衡分子动力学模拟方法研究了单原子LJ流体的非牛顿流变行为,并在系统中分别施加稳态Couette流场和振荡剪切流场.在Couette流场的模拟中,流体出现剪切变稀和法向应力差效应,不同剪切率下的径向分布函数反映了流体分子由于剪切所导致的微观结构变化,通过分析势能函数发现当剪切率增大时,分子间排斥作用增强,吸引作用减弱.在振荡剪切流场的模拟中,发现剪切应力和剪切率之间的相位差随频率增加而增加,随频率增加复数粘度的实部先增大再减小,虚部单调增加,导致虚部粘度相对实部粘度比例增大,弹性模量和粘性模量之比也随频率增加而增加.这三点现象表明LJ流体出现粘弹性行为,且在高频率下,弹性所占比重增大.     

R134a PVT性质的分子动力学模拟

使用二中心LJ分子嵌入沿轴偶极矩(2CLJD)的分子模型,对新型制冷剂R134a的PVT性质进行了分子动力学(MD)模拟,并与实验数据进行了对比,结果表明通过合理地选择势能参数,利用2CLJD模型预测氟利昂类制冷剂的热物理性质是可行的。     

Kr-HF体系的分析势能函数再研究

根据所得到Kr HF体系的两种弱结合分子的结构参数、离解能和谐性力常数 ,采用多体项展式方法 ,对Kr HF体系的性质和势能函数重新进行了研究。导出KrHF(X1Σ+)基态分子的分析势能函数 ,获得KrHF(X1Σ+)体系的势能面。考察了这个势能函数的基本性质 ,准确地复现出Kr HF分子的平衡结构特征     

纳米通道滑移流动的分子动力学模拟研究

本文采用非平衡分子动力学方法对平板纳米通道滑移流动进行了非平衡分子动力学模拟,获得了不同壁面势能和不同温度时流体的速度分布及密度分布。研究结果表明滑移速度在很大程度上决定于流体温度和壁面吸引力作用强度的大小。由于不同壁面吸引力时流体的密度分布受温度的影响规律不同,使得不同壁面吸引力时流体的滑移速度受温度影响规律也不一致。而且,流体结构受壁面流速的影响要受到壁面势能的制约。     

惰性气体晶格中的HF分子的阻碍转动的势能函数

确定了面心立方晶格中线性分子的障碍转动势能函数形式，基于光谱数据中导出惰性气体晶格中的ＨＦ分子的障碍传动势能函数。     

MRCI计算研究B2+分子的结构和解析势能函数

采用从头计算的多参考组态CI方法(MRCI) 和B原子Dunnings相关调和基函数含扩散基的大基组aug-cc-pVQZ对B+2分子的基态和低激发态的势能曲线进行计算 .利用Huxley函数、Murrell-Sorbie函数和最小二乘法拟合出了解析势能函数,并以此为基础计算出光谱常数.通过比较发现:Huxley 函数比MS函数的拟合方差更小,能更好地再现分子中原子间相互作用.采用两种函数所得解析势能函数与从头计算势能曲线间的误差RMS 均远小于化学精度4.184 kJ/mol的要求,表明所得解析势能函数很好地再现了这些态中原子间的相互作用情况,可用于更广泛的研究.     

基态双原子系统的长程势能函数

本文所导出的22个基态双原子分子HFACE势能函数,都具有正确的平衡性质和长程Van der Waals区域正确的渐近性质,表示了完整正确的分子势能曲线。     

用ab initio方法计算NaLi分子基态(X1∑+)的势能函数及光谱常数

运用原子分子群表示方法,首先确定NaLi分子的电子基态(X1∑ ).然后选用6-311 G(3df,2pd)基组优化计算得到NaLi分子基态(X1∑ )的平衡结构和离解能,采用电子相关QCISD(T)方法结合6-311 G(3df,2pd)基组对NaLi分子基态进行单点能扫描计算.最后用单点扫描计算值结合优化计算所得参数去拟合Murrell-Sorbie函数,得到了NaLi分子基态的势能函数.用该势能函数计算的光谱常数与实验结果符合得很好,表明拟合确定的势能函数能精确地描述基态NaLi分子的结构和性质.     

流体粘度的计算机模拟

对流体粘度的计算机模拟作了简单回顾;并利用非平衡分子动力学方法,将在三相点附近的氩看成具有Lennard-Jones势能函数的球形分子,用自编程序对其进行了计算机模拟。     

Dynamic properties of Lennard-Jones fluids and liquid metals

The dependence of the dynamic properties of liquid metals and Lennard-Jones fluids on the characteristics of the interaction potentials is analyzed. Molecular-dynamics simulations of liquids in analogous conditions but assuming that their particles interact either through a Lennard-Jones or a liquid-metal potential were carried out. The Lennard-Jones potentials were chosen so that both the effective size of the particles and the depth of the potential well were very close to those of the liquid-metal potentials. In order to investigate the extent to which the dynamic properties of liquids depend on the short-range attractive interactions as well as on the softness of the potential cores, molecular-dynamics simulations of the same systems but assuming purely repulsive interactions with the same potential cores were also performed. The study includes both single-particle dynamic properties, such as the velocity autocorrelation functions, and collective dynamic properties, such as the intermediate scattering functions, the dynamic structure factors, the longitudinal and transverse current correlations, and the transport coefficients.     

On the suitability of the ILJ function to match different formulations of the electrostatic potential for water-water interactions

Energetic and structural properties of liquid water have been calculated using molecular dynamics simulations in order to investigate the effect of different formulations of the van der Waals (vdW) interaction on the behaviour of liquid water. In particular, two model potentials, the SPC/E using a Lennard Jones (LJ) function and the AMPF using an Improved Lennard Jones function (ILJ) have been considered. The flexibility of the ILJ function in the AMPF model has also been analysed, proving that its vdW component can match different parametrizations of the electrostatic component.     

The volume pinning force for different shapes of the interaction potential between defects and flux lines

The volume pinning force in superconductors with randomly distributed line defects nearly perpendicular to the flux lines is calculated for model as well as realistic interaction potentials between single defects and single flux lines. Both attractive and repulsive interactions defect — flux line were considered. The line defects were constructed from point defects distributed with constant density on straight lines. The deviations of the results from the theory of Labusch are considerable for small elementary interaction forces between defects and flux lines. The deviations (as well as the differences between repulsive and attractive interaction potentials) are larger for the realistic interaction potential than those for the different model potentials. The threshold values for the flux line distortion (under which no net volume pinning can exist) is also given.     

Influence of dispersive long-range interactions on properties of vapour–liquid equilibria and interfaces of binary Lennard-Jones mixtures

The influence of dispersive long-range interactions on properties of vapour–liquid equilibria and interfaces of six binary Lennard-Jones (LJ) mixtures was studied by molecular dynamics (MD) simulations and density gradient theory (DGT). The mixtures were investigated at a constant temperature T, at which the low-boiling component, which is the same in all mixtures, is subcritical. Two different high-boiling components were considered: one is subcritical, the other is supercritical at T. Furthermore, the unlike dispersive interaction was varied such that mixtures with three different types of phase behaviour were obtained: ideal, low-boiling azeotrope, and high-boiling azeotrope. In a first series of simulations, the full LJ potential was used to describe these mixtures. To assess the influence of the long-range interactions, these results were compared with simulations carried out with the LJ truncated and shifted (LJTS) potential applying the corresponding states principle. The dispersive long-range interactions have a significant influence on the surface tension and the interfacial thickness of the studied mixtures, whereas the relative adsorption and the enrichment are hardly affected. Furthermore, the influence of the long-range interactions on Henry's law constants and the phase envelopes of the vapour–liquid equilibrium was investigated. The long-range interactions have practically no influence on the composition dependency of the investigated mixture properties.     

Microrheological consequences of attractive colloid-colloid potentials in a two-dimensional Brownian fluid

By using microrheological methods commonly employed in videomicroscopy experiments, we study the rheology of a two-dimensional computational fluid formed by Brownian disks with the aim of exploring the influence of some effective colloid-colloid attractive interactions. The model of fluid is developed by Brownian dynamics simulations without hydrodynamical interactions, and it is characterized by calculating its equation of state from the pair distribution function. Micromechanical properties, relative and intrinsic viscosity and freezing are discussed. Then, we include attractive forces such a Asakura-Oosawa depletion force or an empiric expression proposed by Grier and Hal (GH) for an anomalous electrostatic potential observed in confined and charged colloids. By using both potentials, viscosity is clearly increased, but when the GH potential is included, viscoelastic gel state is reached for intermediate values of surface concentration. Finally, we analyse the influence of the attractive potentials in the breaking-up by thermal fluctuations of linear chains formed by 2D particles, finding that the GH potential reduces the characteristical time at which the disks can be considered as disaggregated. In this work, we employ an experimental-like methodology for the study of a Brownian hard-disk fluid, providing a very useful link with experimental procedures.     

自由能方法与零压下Al的熔化温度

利用自由能方法的分子动力学模拟,计算了零压下Al的熔化温度.在计算液相自由能的过程中,采用勒纳-琼斯(LJ)液体作为参考系统,同时将计算结果与Mei和Davenport等人的计算结果进行了比较,计算结果表明：1)选用LJ参考系统使液相自由能的计算时间节省一半,并且不影响熔化温度的计算结果;2)采用不同的埋入原子势(EAM)的分子动力学模拟计算得到的熔化温度与实验值都存在偏差,而就金属Al而言,采用Cai等人的EAM势的熔化温度的计算结果比Mei和Davenport及Morris等人采用的势模型的结果略有改 关键词： 熔化温度 自由能方法 分子动力学模拟     

Influence of polymer-pore interactions on translocation

We investigate the influence of polymer-pore interactions on the translocation dynamics using Langevin dynamics simulations. An attractive interaction can greatly improve the translocation probability. At the same time, it also increases the translocation time slowly for a weak attraction while an exponential dependence is observed for a strong attraction. For fixed driving force and chain length the histogram of translocation time has a transition from Gaussian distribution to long-tailed distribution with increasing attraction. Under a weak driving force and a strong attractive force, both the translocation time and the residence time in the pore show a nonmonotonic behavior as a function of the chain length. Our simulations results are in good agreement with recent experimental data.     

Influence of the long-range forces in non-Gaussian random-packing dynamics

In this paper, we perform molecular dynamics (MD) simulations to study the random packing of spheres with different particle size distributions. In particular, we deal with non-Gaussian distributions by means of the Lévy distributions. The initial positions as well as the radii of five thousand non-overlapping particles are assigned inside a confining rectangular box. After that, the system is allowed to settle under gravity towards the bottom of the box. Both the translational and rotational movements of each particle are considered in the simulations. In order to deal with interacting particles, we take into account both the contact and long-range cohesive forces. The normal viscoelastic force is calculated according to the nonlinear Hertz model, whereas the tangential force is calculated through an accurate nonlinear-spring model. Assuming a molecular approach, we account for the long-range cohesive forces using a Lennard-Jones (LJ)-like potential. The packing processes are studied assuming different long-range interaction strengths.     

Adhesion hysteresis in dynamic atomic force microscopy

The effects of adhesion hysteresis in the dynamic‐dissipation curves measured in amplitude‐modulation atomic force microscopy are discussed. Hysteresis in the interaction forces is shown to modify the dynamics of the cantilever leading to different power dissipation curves in the repulsive and attractive regimes. Experimental results together with numerical simulations show that power dissipation, as measured in force microscopy, is not always proportional to the energy dissipated in the tip–sample interaction process. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Semi-flexible polymers with attractive interactions

The delocalization and unbinding transitions of two semi-flexible polymers which experience attractive interactions are studied by a variety of theoretical methods. In two-dimensional systems, one has to distinguish four different universality classes for the interaction potentials. In particular, the delocalization transitions from a potential well and the unbinding transitions from such a well in the presence of a hard wall exhibit distinct critical behavior governed by different critical exponents. In three-dimensional systems, we predict first-order transitions with a jump in the energy density but with critical or self-similar fluctuations leading to distribution functions with power law tails. The predicted critical behavior is confirmed numerically by transfer matrix calculations in two dimensions and by Monte Carlo simulations in three dimensions. This behavior should be accessible to experiments on biopolymers such as actin filaments or microtubuli. Received 15 December 1999 and Received in final form 19 May 2000