Surface effects in simple molecular systems

This thesis examines two problems concerned with surface effects in simple molecular systems. The first is the problem associated with the interaction of a fluid with a solid boundary, and the second originates from the interaction of a liquid with its own vapor.

For a fluid in contact with a solid wall, two sets of integro-differential equations, involving the molecular distribution functions of the system, are derived. One of these is a particular form of the well-known Bogolyubov-Born-Green-Kirkwood-Yvon equations. For the second set, the derivation, in contrast with the formulation of the B.B.G.K.Y. hierarchy, is independent of the pair-potential assumption. The density of the fluid, expressed as a power series in the uniform fluid density, is obtained by solving these equations under the requirement that the wall be ideal.

The liquid-vapor interface is analyzed with the aid of equations that describe the density and pair-correlation function. These equations are simplified and then solved by employing the superposition and the low vapor density approximations. The solutions are substituted into formulas for the surface energy and surface tension, and numerical results are obtained for selected systems. Finally, the liquid-vapor system near the critical point is examined by means of the lowest order B.B.G.K.Y. equation.

Yb：Ca5（PO4）3F激光晶体的生长缺陷

采用提拉法生长了质量优异的Yb：Ca5（PO4）2F（Yb：FAP）晶体。运用化学腐蚀，光学显微镜、扫描电子显微镜以及能量散射光谱仪观察了该晶体中的生长条纹和包裹物等宏观缺陷，以及晶体的位错腐蚀形貌、位错密度及其分布情况，同时观察了晶体中亚晶界的形态。由晶体中位错的径向变化以及生长条纹可知：晶体在生长过程中为微凸界面生长。高温下CaF2的挥发造成了在晶体生长后期熔体中组分偏离化学计量比，出现组分过冷，形成包裹物。且位错密度显著增加。Yb：FAP晶体的各向异性使得晶体在（10 10）面的位错蚀坑形状、大小以

伦纳德琼斯薄膜材料导热系数的分子动力学研究

提出从微观的角度,借助计算机工具,将薄膜破坏发展的细节展现出来的分子动力学研究的思想。使得实验上难以观察的现象变得形象而便于理解。应用分子动力学理论,使用伦纳德琼斯势函数,采用预校正积分法和虚拟外力约束标定方法,模拟薄膜体系的传热系数受体系的密度、温度的影响,同时结合体系粒子的径向分布函数和长程分布函数分析了相应的系统结构特性。另外,采用不同的模拟尺寸获得了低维材料所特有的“高温尺寸效应”。结果显示,导热系数随密度的增加变大,随温度的上升而变大。这些数据现有测量手段是难以得到的,这类模拟可以为研究提供一些

Multimode radiation from an unflanged, semi-infinite circular duct with uniform flow.

Multimode sound radiation from an unflanged, semi-infinite, rigid-walled circular duct with uniform subsonic mean flow everywhere is investigated theoretically. The multimode directivity depends on the amplitude and directivity function of each individual cut-on mode. The amplitude of each mode is expressed as a function of cut-on ratio for a uniform distribution of incoherent monopoles, a uniform distribution of incoherent axial dipoles, and for equal power per mode. The directivity function of each mode is obtained by applying a Lorentz transformation to the zero-flow directivity function, which is given by a Wiener-Hopf solution. This exact numerical result is compared to an analytic solution, valid in the high-frequency limit, for multimode directivity with uniform flow. The high-frequency asymptotic solution is derived assuming total transmission of power at the open end of the duct, and gives the multimode directivity function with flow in the forward arc for a general family of mode amplitude distribution functions. At high frequencies the agreement between the exact and asymptotic solutions is shown to be excellent.

High frequency multimode radiation from ducts with flow

Multimode sound radiation from hard-walled semi-infinite ducts with uniform subsonic flow is investigated theoretically. An analytic expression, valid in the high frequency limit, is derived for the multimode directivity function in the forward arc for a general family of mode distribution functions. The multimode directivity depends on the amplitude and directivity function of each individual mode. The amplitude of each mode is expressed as a function of cut-off ratio for a uniform distribution of incoherent monopoles, a uniform distribution of incoherent axial dipoles and for equal power per mode. The modes' directivity functions are obtained analytically by applying a Lorentz transformation to the zero flow solution. The analytic formula for the multimode directivity with flow is derived assuming total transmission of power at the open-end of the duct. This formula is compared to the exact numerical result for an unflanged duct, computed utilizing a Wiener-Hopf solution. The agreement is shown to be excellent. Copyright © 2008 by the American Institute of Aeronautics and Astronautics, Inc. All rights reserved.

Numerical computation of laminar flow in a heated rotating cavity with an axial throughflow of air

A heated rotating cavity with an axial throughflow of cooling air is used as a model for the flow in the cylindrical cavities between adjacent discs of a high-pressure gas-turbine compressor. In an engine the flow is expected to be turbulent, the limitations of this laminar study are fully realised but it is considered an essential step to understand the fundamental nature of the flow. The three-dimensional, time-dependent governing equations are solved using a code based on the finite volume technique and a multigrid algorithm. The computed flow structure shows that flow enters the cavity in one or more radial arms and then forms regions of cyclonic and anticyclonic circulation. This basic flow structure is consistent with existing experimental evidence obtained from flow visualization. The flow structure also undergoes cyclic changes with time. For example, a single radial arm, and pair of recirculation regions can commute to two radial arms and two pairs of recirculation regions and then revert back to one. The flow structure inside the cavity is found to be heavily influenced by the radial distribution of surface temperature imposed on the discs. As the radial location of the maximum disc temperature moves radially outward, this appears to increase the number of radial arms and pairs of recirculation regions (from one to three for the distributions considered here). If the peripheral shroud is also heated there appear to be many radial arms which exchange fluid with a strong cyclonic flow adjacent to the shroud. One surface temperature distribution is studied in detail and profiles of the relative tangential and radial velocities are presented. The disc heat transfer is also found to be influenced by the disc surface temperature distribution. It is also found that the computed Nusselt numbers are in reasonable accord over most of the disc surface with a correlation found from previous experimental measurements. © 1994, MCB UP Limited.

Free energy surface reconstruction from umbrella samples using Gaussian process regression II: Multiple collective variables

We demonstrate how a prior assumption of smoothness can be used to enhance the reconstruction of free energy profiles from multiple umbrella sampling simulations using the Bayesian Gaussian process regression approach. The method we derive allows the concurrent use of histograms and free energy gradients and can easily be extended to include further data. In Part I we review the necessary theory and test the method for one collective variable. We demonstrate improved performance with respect to the weighted histogram analysis method and obtain meaningful error bars without any significant additional computation. In Part II we consider the case of multiple collective variables and compare to a reconstruction using least squares fitting of radial basis functions. We find substantial improvements in the regimes of spatially sparse data or short sampling trajectories. A software implementation is made available on www.libatoms.org.

Ni silicide nanowires analysis by atom probe tomography

The Ni silicide formed at low temperature on Si nanowire has been analyzed by atom probe tomography (APT) thanks to a special technique for sample preparation. A method of preparation has been developed using the focused ion beam (FIB) for the APT analysis of nanowires (NWs). This method allow for the measurement of the radial distribution when a NW is cut, buried in a protective metal matrix, and finally mounted on the APT support post. This method was used for phosphorous doped Si NWs with or without a silicide shell, and allows obtaining the concentration and distribution of chemical elements in three-dimensions (3D) in the radial direction of the NWs. The distribution of atoms in the NWs has been measured including dopants and Au contamination. These measurements show that δ-Ni2Si phase is formed on Si NW, Au is found as cluster at the Ni/δ-Ni2Si interface and P is segregated at the δ-Ni2Si/ Si NW interface. The results obtained on NWs after silicidation were compared with the silicide on the Si substrate, showing that the same silicide phase δ-Ni2Si formed in both cases (NWs and substrate). © 2013 Elsevier B.V. All rights reserved.

紫花苜蓿不同根系分布模式的土壤水分模拟和验证

根系分布影响着土壤水分养分吸收,实测根系分布费时费力,经验根系分布函数参数简单,应用方便。该研究在田间采用苜蓿栽培土柱试验,测定根系分布,并将其和不同经验根系分布函数分别应用于Hydrus-1D对土壤水分进行动态模拟,通过土壤水分实测值和模拟值比较,验证分析了经验根系分布函数的适用性以及对土壤水分动态变化的影响。结果表明:拟合的根系分布、Prasad分布、Hoffman和van Genuchten分布3种根系分布函数的根长密度模拟值与36cm以下的根长密度实测值较为吻合,Raats根系分布模拟值与实测值及其他分布函数则差别较大。不同根系分布下土壤水分模拟差别不大,平均相对均方根误差在3.5%以下。非胁迫生长条件下,Prasad根系分布、Hoffman和vanGenuchten根系分布都可描述紫花苜蓿实际根系分布状况。

ELECTRONIC AND MAGNETIC-STRUCTURE OF THE TERNARY COMPOUND ND2FE17N

The electronic and the magnetic structure of the Nd2Fe17N1 phase in the family of Nd-Fe-N ternary compounds have been calculated using the first-principles, spin-polarized orthogonalized linear-combination-of-atomic-orbitals method. Results are presented in the form of site-decomposed and spin-projected partial density of states. The occupation sites of the three N atoms are determined by an average radial distribution of all possible N site configurations. Both cases of N occupying the 3b and the 18g sites are studied. The results indicate that the 6c Fe sites have the maximum and the 18h Fe sites have the minimum local moments. This is in good agreement with experiment. It is concluded that the influence on the local moment due to lattice expansion is less important compared to that due to interatomic interaction between the N atom and its neighbors. The results also show the important role of N atoms in raising the Curie temperature of this compound.

Molecular dynamics simulation of polystyrene-block-poly(methyl methacrylate)

Molecular dynamics is applied to the system of polystyrene-block-poly(methyl methacrylate). The simulation shows that for the block copolymer system, a layered structure, which reflects microphase separation, is obtained and this structure is stable. In order to elucidate that the formation of the layered structure is reasonable, some static properties such as the radial distribution function and the dipole moment are analyzed in some detail.

STRUCTURE-ANALYSIS OF MOLTEN CACL2-KCL SYSTEM BY X-RAY-DIFFRACTION

Radial distribution function of CaCl2-KCl (1:2 mol) melt was measured by X-ray scattering of high temperature liquid. The nearest neighbour distances of Ca2+-Cl-, K+-Cl- and Cl--Cl- ionic pairs are 0.278, 0.306 and 0.380 nm, respectively, Discussion on the relation between structure and physicochemical properties in the melt was simply done in this paper.

笼形水簇和溶解甲烷之间平均力势能的约束型分子动力学计算及其在天然气水合物成核研究中的意义

That the dodecahedral water cluster (DWC) can adsorb dissolved methane molecules, an important phenomenon related to the hydrate nucleation study, has been observed through molecular dynamics simulations, but it has not been explained satisfactorily [Guang-Jun Guo; Yi-Gang Zhang; Hua Liu. J. Phys. Chem. C, 2007, 111, 2595]. In order to explain this phenomenon by using the potential of mean force (PMF) between the DWC and the dissolved methane, we perform several series of constrained molecular dynamics simulations in the methane-water system. The distance between the center of DWC and the methane molecule is constrained from 5 Å to 18 Å by adding 0.2 Å every time. For each fixed distance, we perform 20 independent simulations to improve the statistical precision. We first get the constraint force between the DWC and the dissolved methane in each simulation and then calculate the PMF by integrating these forces. Subsequently, the radial distribution function (RDF) is obtained from the PMF through an equation of statistical mechanics. The results show that the RDF has a sharp peak at about 6.2 Å, successfully explaining why the DWC adsorbs dissolved methane molecules. The preferential binding coefficient is a positive value (=2.05±0.5), indicates that the DWC tends to adsorb dissolved methane rather than water molecules in methane aqueous solutions. The curve of PMF for the DWC encaging a methane almost coincides that for the empty DWC, meaning that it is the DWC rather than the encaged methane who could adsorb dissolved methane molecules. By comparing the curves of PMF for different directions of the DWC relative to the dissolved methane, we find that it is the cage face rather than the cage edge or vertex that plays an essential role when the DWC adsorbing dissolved methane. This research sheds light on the driving force for the methane adsorption, and it is helpful in understanding the nucleation process of methane hydrate.

A Theory of Networks for Appxoimation and Learning

Learning an input-output mapping from a set of examples, of the type that many neural networks have been constructed to perform, can be regarded as synthesizing an approximation of a multi-dimensional function, that is solving the problem of hypersurface reconstruction. From this point of view, this form of learning is closely related to classical approximation techniques, such as generalized splines and regularization theory. This paper considers the problems of an exact representation and, in more detail, of the approximation of linear and nolinear mappings in terms of simpler functions of fewer variables. Kolmogorov's theorem concerning the representation of functions of several variables in terms of functions of one variable turns out to be almost irrelevant in the context of networks for learning. We develop a theoretical framework for approximation based on regularization techniques that leads to a class of three-layer networks that we call Generalized Radial Basis Functions (GRBF), since they are mathematically related to the well-known Radial Basis Functions, mainly used for strict interpolation tasks. GRBF networks are not only equivalent to generalized splines, but are also closely related to pattern recognition methods such as Parzen windows and potential functions and to several neural network algorithms, such as Kanerva's associative memory, backpropagation and Kohonen's topology preserving map. They also have an interesting interpretation in terms of prototypes that are synthesized and optimally combined during the learning stage. The paper introduces several extensions and applications of the technique and discusses intriguing analogies with neurobiological data.

A Connection Between GRBF and MLP

Both multilayer perceptrons (MLP) and Generalized Radial Basis Functions (GRBF) have good approximation properties, theoretically and experimentally. Are they related? The main point of this paper is to show that for normalized inputs, multilayer perceptron networks are radial function networks (albeit with a non-standard radial function). This provides an interpretation of the weights w as centers t of the radial function network, and therefore as equivalent to templates. This insight may be useful for practical applications, including better initialization procedures for MLP. In the remainder of the paper, we discuss the relation between the radial functions that correspond to the sigmoid for normalized inputs and well-behaved radial basis functions, such as the Gaussian. In particular, we observe that the radial function associated with the sigmoid is an activation function that is good approximation to Gaussian basis functions for a range of values of the bias parameter. The implication is that a MLP network can always simulate a Gaussian GRBF network (with the same number of units but less parameters); the converse is true only for certain values of the bias parameter. Numerical experiments indicate that this constraint is not always satisfied in practice by MLP networks trained with backpropagation. Multiscale GRBF networks, on the other hand, can approximate MLP networks with a similar number of parameters.