玻璃化转变的分子串模型中分子串弛豫模式的计算机模拟

基于玻璃化转变的分子串模型的哈密顿量(Hamiltonian),提出了模拟分子串第一和第二弛豫模式的蒙特卡罗(Monte Carlo)模拟方案.模拟得出的第一和第二弛豫模式的弛豫时间,与分子串模型中分子串弛豫方程所预言的结果完全一致,即理论预期和模拟结果相互印证.这不仅说明了分子串模型的分子串弛豫方程、至少是第一和第二弛豫模式的理论预言的正确性,同时也表明了本文所提出的模拟方法的有效性,并进一步明晰了分子串中分子的随机涨落和跃迁运动的图像,也为三态甚至是多态的分子串弛豫动力学研究,以及对进一步模拟分子串之 关键词： 弛豫动力学 蒙特卡罗模拟 分子串     

分子串模型中空间弛豫模式的弛豫动力学的蒙特卡罗模拟

基于玻璃化转变的分子串模型的分子串弛豫方程,提出了更为精确的模拟分子串中所有空间弛豫模式(SRM)的蒙特卡罗模拟方案. 模拟得出各个SRM的弛豫时间随温度和分子串长度的变化结果与分子串模型中分子串弛豫方程的预言完全一致,即理论预期和模拟结果相互印证. 应当指出,分子串能否作为液态中集体单元的必要条件是在考虑到分子串之间的不均匀随机相互作用后,分子串的所有SRM的定性特征是不能改变的,这就需要对不同分子串的SRM之间的耦合进行研究. 但是迄今为止,仍未发现相关的严格解,仅有近似的自洽弛豫平均场方法. 由此可知,所提出的模拟方案为研究不同分子串的SRM之间的耦合(包括上述自洽场的可行性)提供了必要的基础. 关键词： 玻璃化转变 弛豫动力学 蒙特卡罗模拟 分子串     

磷脂微滴囊泡化的介观模拟

发展了一种非显示溶剂的粗粒化三粒子磷脂模型,该模型明确反映磷脂分子的双尾结构．模型分别采用变形的MIE作用势和Harmonic作用势描述分子间非成键和分子内成键相互作用,粗粒化力场参数通过拟合DPPC双分子层的结构和力学性质获得．该粗粒化模型成功重现了磷脂分子从随机初始态到双分子层和从盘状结构到囊泡的形成过程．应用该模型系统研究了球形和柱形磷脂微滴囊泡化的过程,结果表明此模型能有效地模拟介观尺度下复杂磷脂囊泡的形成及演化．     

多腔体复杂系统电磁脉冲耦合统计特性

以双腔体级联系统为实验对象,测量了系统的输出端感应电压,对实验结果进行统计分析,并与随机拓扑模型计算结果进行对比,两者基本吻合,验证了随机拓扑模型的适用性;利用该模型计算分析了不同脉冲参数及不同拓扑结构条件下多混沌腔体复杂系统的电磁耦合统计特性。研究表明,脉冲宽度和脉冲个数与概率峰值处的感应电压均存在一定的谐振特性,且脉冲频率越低,脉冲的耦合效率越高,采用串型的拓扑结构更加有利于系统的防护和加固。     

RbCl键取向序的分子动力学模拟

进行T=80,300,1023K晶态和熔融态RbCI的分子动力学模拟,并对模拟结果进行了键序参数分析.模拟表明,采用Fumi-Tosi形式的两体有效势与Dixon和Sangster给出的势参数,可很好地重复EXAFS和中子散射实验结果.熔融RbCI中的键取向序,可很好地用两结构模型来描述,简单立方局部结构约占65%,正四面体占35%.通过两结构模型对径向分布函数非对称展宽、配位数、键角分布和粘度作了讨论. 关键词：     

向列型液晶的硬棒理论与分子取向短程关联

在向列型液晶的硬棒理论中引入分子取向短程关联。理论的出发点是Ｓｉｎ－ＤｏｏＬｅｅ的自由能表示，这一表示基于Ｃａｒｎａｈａｎ－Ｓｔａｒｌｉｎｇ状态方程。用包括了分子短程关联的取向熵代替原来平均场形式的取向熵项，得到新的自由能表示。通过自由能对分子取向分布求变分确定平衡态分布。对液晶ＰＡＡ进行了数值计算。给出了相变点序参数、熵变、相变点致密度和相对密度变化的计算值。考虑短程关联后的理论值较通常硬棒理论有显著改进。因此，在某种程度上克服了硬棒理论的困难。     

SiGe HBT大信号等效电路模型

基于SiGe HBT(异质结双极晶体管)的物理模型，建立了描述SiGe HBT的大信号等效电路模型.该等效电路模型考虑了准饱和效应和自热效应等，模型分为本征和非本征两部分，物理意义清晰，拓扑结构相对简单.该模型嵌入了PSPICE软件的DEVEO(器件方程开发包)中.在PSPICE软件资源的支持下，利用该模型对SiGe HBT器件进行了交直流特性模拟分析，模拟结果与理论分析结果相一致，并且与文献报道的结果符合较好. 关键词： SiGe HBT 等效电路模型 PSPICE     

C60分子在有序-无序和玻璃态相变间的取向概率与弛豫行为

用极限动力学模型研究了C60分子在有序-无序相变和玻璃态相变温度区间取向角为98°和38°的取向概率与温度的关系.计算结果在玻璃态相变点附近的85!K,90!K和有序-无序相变点的260!K分别与实验值相吻合,取向概率对实验值更精确的拟合及其对温度的二阶导数预言玻璃态相变点在84!K.导出了弛豫规律,其结果表明:双能级的C60分子从非平衡态到平衡态的弛豫行为与非指数因子β有关,其总的弛豫时间决定于其中一个较短的弛豫时间,展宽指数形式保持不变.讨论了KWW方程的非指数因子β与分子间协同作用的关系,发现与双取向态间的能级差有关,计算值与实验结果相同.     

磁场作用下向列型液晶中的分子取向短程关联

从分子统计理论的观点研究磁场对向列型液晶的作用。将向列型液晶的格胞理论推广到包含磁场作用的情况。这一理论考虑了分子取向短程关联。向列相序参数对约化温度的依赖关系和每个分子的约化内能对约化温度的依赖关系，与计算机模拟结果符合得相当好。计算了各向同性相最低过冷温度，理论结果与实验值和分子场理论的结果进行了比较。     

分子动力学模拟钠硼硅酸盐玻璃电子辐照诱导的结构演化效应

钠硼硅酸盐玻璃作为高放射废物玻璃固化体的候选材料之一,已有大量实验对该类玻璃开展了电子或重离子的辐照效应研究.然而,在理论计算与模拟方面的工作却很少,目前主要集中于重离子的辐照效应,对电子的辐照效应的模拟尚未见报道.本文利用分子动力学工具提出一种新的方法,以实现对电子辐照诱导的玻璃结构演化进行模拟.该方法基于实验中玻璃的结构变化特点,即实验中的拉曼结果已经证实:在大剂量的电子辐照后的玻璃中存在分子氧的事实,由于这些分子氧不会与其他粒子发生相互作用,因而可以通过从体系中逐步地移除一定数量氧原子的方式,以达到模拟大剂量电子辐照的情形,进而得到电子辐照后的玻璃的结构信息.模拟结果显示:随着移除氧原子的数量增加,玻璃中的Si—O—Si平均键角逐渐减小;而且玻璃中的小环数量会因氧的逐渐减少而逐渐增加;玻璃中部分[BO4]结构会转变为[BO3]结构,最终这种转变会达到饱和;大量移除氧之后,玻璃中的钠元素也出现明显的相分离.这些模拟辐照的玻璃结构特性能较好地与实验中的硼硅酸盐玻璃电子辐照诱导的结构变化符合.因此,本文提出的方法有望为通过分子动力学模拟硼硅酸盐玻璃的电子辐照效应提供新思路.     

Universal power law in the orientational relaxation in thermotropic liquid crystals

We observe a surprisingly general power law decay at short to intermediate times in orientational relaxation in a variety of model systems (both calamitic and discotic, and also lattice) for thermotropic liquid crystals. As all these systems transit across the isotropic-nematic phase boundary, two power law relaxation regimes, separated by a plateau, emerge, giving rise to a steplike feature (well known in glassy liquids) in the single-particle second-rank orientational time correlation function. In contrast to its probable dynamical origin in supercooled liquids, we show that the power law here can originate from the thermodynamic fluctuations of the orientational order parameter, driven by the rapid growth in the second-rank orientational correlation length.     

Molecular dynamics simulations of the orientational motion of liquid chloroform at 298 K and 220K

Molecular dynamics simulations of liquid chloroform at 298 K and 220 K, using established optimized potential parameters and run on single-processor workstations, are employed to compute the first- and second-order Legendre polynomial, single-molecule orientational correlation functions describing the tumbling motion of the carbon-hydrogen bond direction. The results of the simulated Raman correlation functions compare well with their experimental counterparts from previously reported Fourier-transformed band contours of two totally symmetric vibration-rotation modes of the liquid. Simulated angular momentum, angular velocity, and intermolecular torque correlation functions are shown, and helped to characterize the insignificance of free orientational mobility within the system. Perturbation effects from rotation-vibration interaction and collision-induced intensities are present, but their effects on the correlation results are not sufficiently high to be of major significance.     

Scaling properties of dynamic response in orientational glasses

The freezing transition in dipolar and quadrupolar glasses is characterized by the presence of local random electric and strain fields generated by substitutional disorder. The dynamic response in the ergodic phase above the freezing temperature T_F is studied in terms of Langevin dynamics applied to the recently formulated symmetry-adapted random-bond-random-field (SARBRF) model of orientational glasses. Following the theory of spin glasses it is assumed that for T≥T_F the response can be written in a dynamic scaling form by introducing a scaling exponent v and a frequency scaling variable. The value of v(T) is explicitly evaluated for the quadrupolar (100) SARBRF model, and its relation to the experimentally observed effective exponent u_eFF(T) in dipolar and quadrupolar glasses is discussed.     

On the calculation of the orientational correlation parameter g 2

The g ₂ factor for a model of liquid carbon disulphide has been calculated by molecular dynamics simulation. The values of g ₂ for the model at three points along the orthobaric curve are: 1·17 ± 0·04 (298 K), 1·27 ± 0·03 (245 K), 1·39 ± 0·06 (193 K). These values are in good agreement with available experimental values. By calculating g ₂ in shells of cubic symmetry it is found that the value of g ₂ is determined by the orientational correlation of a molecule with neighbours within a few (two to three) molecular diameters. Spurious orientational correlations are introduced by the periodic boundary conditions and the calculation of collective correlation functions by averaging over the whole cube is shown to be unreliable. A theoretical calculation of g ₂ using RISM + SSA fails to reproduce the state dependence of the g ₂ values calculated from the simulation. This failure is not due to the small differences between the simulation and RISM g _αβ(r) for r < 4·5 Å but to inaccuracies in the SSA in the intermediate region r ～ 6 Å.     

Dipole orientational order at liquid/vapor surfaces

We present ellipsometric observations of the orientational order alpha(2) of highly polar molecules at the noncritical liquid/vapor surface of critical polar+nonpolar mixtures. The dipoles, which are repelled from the interface via interactions with their image dipoles, are preferentially oriented with their axes parallel to the surface and possess an orientational order which is well described by alpha(2) approximately -t(2beta)D+(z/xi), where t=[T-T(c)]/T(c) is the reduced temperature, beta=0.328 is a critical exponent, and D+ is a universal function of the dimensionless depth z/xi with surface correlation length xi.     

Critical properties at the orientational first order transition in solid o-H2 in MFA

The mean field approximation (MFA) is used to study critical phenomena in the orientational transition of solid o-H₂. The time independent correlations as well as the time dependent ones, calculated within the Glauber model, show critical behaviour at the stability limits of the ordered and disordered phase with critical indices 1/2 and 1 resp. At the equilibrium transition point the correlation lengths and relaxation times of both phases are found to be equal.     

Bond orientational order in atomic clusters

Bond orientational order parameters for the global minimum energy configurations of a number of Lennard-Jones and Morse clusters are calculated. The results demonstrate that the bond orientational order parameters, particularly the third-order invariants, provide a fairly discriminating set of symmetry markers for different cluster geometries. Since they are relatively easy to calculate from simulation data, they may be useful in studies of local order in a wide variety of contexts, including studies of melting, nucleation and the glass transition     

Investigation of the orientational correlation of the molecules in liquid H2S with reverse Monte Carlo simulation

Reverse Monte Carlo simulation of liquid H₂S has been performed on the basis of an X-ray and a neutron diffraction experiment, and the resulting structure is analysed in detail. Partial pair correlation functions, spatial distribution of the molecules around each other and the preferred relative orientation of the nearest neighbours are investigated. The orientational correlation of the molecules is discussed in terms of the coefficients of the spherical harmonic expansion of the orientational pair correlation function. It is found that H₂S is not a closely packed liquid: the average first-shell coordination number of the molecules is about 8. This is found to be a direct consequence of the molecular shape, i.e., the excluded volume of the H atoms prevents the central molecule from being surrounded by more first-shell neighbours. The relative orientation of the molecules is found to be almost completely uncorrelated. Moreover, even the existing small correlation is confined to a rather small distance range and vanishes beyond about the third nearest neighbour.     

Azimuthal orientational correlations due to excluded volume epitaxy in growing anisotropic grains

The microstructure of anisotropically shaped grains can strongly influence a range of material properties, including transport, mechanical and electro-optical. A grain-structure-related phenomenon, known as excluded volume epitaxy (EVE), is reported in this study. EVE is a local, inter-grain orientational correlations effect, which results from a combination of continuous nucleation of anisotropic grains and impingement of growing grains. Due to EVE, anisotropically shaped grains have a tendency to be similarly aligned in a local neighbourhood, despite the absence of any forced global orientation in the sample. The effect has been repeatedly observed by the authors in block copolymers, as illustrated by a representative TEM image. Optical microscopy of anisotropically shaped non-polymeric crystals revealed the generality of this effect. The simulation study revealed a tendency for azimuthal, inter-grain orientational correlation and re-confirmed the experimental observation of EVE.     

A statistical theory of orientational ordering at the free surface of a liquid of ellipsoidal molecules

The surface tension γ of a system of ellipsoidal molecules is evaluated approximately using a generalized Fowler-Kirkwood-Buff model. The pair potential is modelled as u(r/σ) where r is the centre of mass distance and σ is an angle dependent range parameter determined by the shape anisotropy of the molecule. It is shown that if the pair correlation function g scales as g(r/σ) γ can be mapped onto the value for a system of spheres, multiplied by an angular integral which takes into account approximately both the anisotropic molecular shape as well as possible orientational order. It is shown that γ is lowered when the orientational order parameter Q ≠ 0, implying that isotropic molecular liquids may be partially ordered near the free surface. The surface favours parallel ordering of rod-like particles in a direction in the plane of the surface. For plate-like particles, ordering with the plates in the plane of the surface is favoured. In both cases the anchoring energies increase sharply with the shape anisotropy of the molecule. These results are qualitatively consistent with the surface properties of non-polar nematic liquid crystals.