Theoretical investigation of mechanisms of formation and interaction of nanoparticles

In this thesis an investigation into theoretical models for formation and interaction of nanoparticles is presented. The work presented includes a literature review of current models followed by a series of five chapters of original research. This thesis has been submitted in partial fulfilment of the requirements for the degree of doctor of philosophy by publication and therefore each of the five chapters consist of a peer-reviewed journal article. The thesis is then concluded with a discussion of what has been achieved during the PhD candidature, the potential applications for this research and ways in which the research could be extended in the future. In this thesis we explore stochastic models pertaining to the interaction and evolution mechanisms of nanoparticles. In particular, we explore in depth the stochastic evaporation of molecules due to thermal activation and its ultimate effect on nanoparticles sizes and concentrations. Secondly, we analyse the thermal vibrations of nanoparticles suspended in a fluid and subject to standing oscillating drag forces (as would occur in a standing sound wave) and finally on lattice surfaces in the presence of high heat gradients. We have described in this thesis a number of new models for the description of multicompartment networks joined by a multiple, stochastically evaporating, links. The primary motivation for this work is in the description of thermal fragmentation in which multiple molecules holding parts of a carbonaceous nanoparticle may evaporate. Ultimately, these models predict the rate at which the network or aggregate fragments into smaller networks/aggregates and with what aggregate size distribution. The models are highly analytic and describe the fragmentation of a link holding multiple bonds using Markov processes that best describe different physical situations and these processes have been analysed using a number of mathematical methods. The fragmentation of the network/aggregate is then predicted using combinatorial arguments. Whilst there is some scepticism in the scientific community pertaining to the proposed mechanism of thermal fragmentation,we have presented compelling evidence in this thesis supporting the currently proposed mechanism and shown that our models can accurately match experimental results. This was achieved using a realistic simulation of the fragmentation of the fractal carbonaceous aggregate structure using our models. Furthermore, in this thesis a method of manipulation using acoustic standing waves is investigated. In our investigation we analysed the effect of frequency and particle size on the ability for the particle to be manipulated by means of a standing acoustic wave. In our results, we report the existence of a critical frequency for a particular particle size. This frequency is inversely proportional to the Stokes time of the particle in the fluid. We also find that for large frequencies the subtle Brownian motion of even larger particles plays a significant role in the efficacy of the manipulation. This is due to the decreasing size of the boundary layer between acoustic nodes. Our model utilises a multiple time scale approach to calculating the long term effects of the standing acoustic field on the particles that are interacting with the sound. These effects are then combined with the effects of Brownian motion in order to obtain a complete mathematical description of the particle dynamics in such acoustic fields. Finally, in this thesis, we develop a numerical routine for the description of "thermal tweezers". Currently, the technique of thermal tweezers is predominantly theoretical however there has been a handful of successful experiments which demonstrate the effect it practise. Thermal tweezers is the name given to the way in which particles can be easily manipulated on a lattice surface by careful selection of a heat distribution over the surface. Typically, the theoretical simulations of the effect can be rather time consuming with supercomputer facilities processing data over days or even weeks. Our alternative numerical method for the simulation of particle distributions pertaining to the thermal tweezers effect use the Fokker-Planck equation to derive a quick numerical method for the calculation of the effective diffusion constant as a result of the lattice and the temperature. We then use this diffusion constant and solve the diffusion equation numerically using the finite volume method. This saves the algorithm from calculating many individual particle trajectories since it is describes the flow of the probability distribution of particles in a continuous manner. The alternative method that is outlined in this thesis can produce a larger quantity of accurate results on a household PC in a matter of hours which is much better than was previously achieveable.

Supersolid and solitonic phases in the one-dimensional extended Bose-Hubbard model

We report our findings on the quantum phase transitions in cold bosonic atoms in a one-dimensional optical lattice using the finite-size density-matrix renormalization-group method in the framework of the extended Bose-Hubbard model. We consider wide ranges of values for the filling factors and the nearest-neighbor interactions. At commensurate fillings, we obtain two different types of charge-density wave phases and a Mott insulator phase. However, departure from commensurate fillings yields the exotic supersolid phase where both the crystalline and the superfluid orders coexist. In addition, we obtain the signatures for the solitary waves and the superfluid phase.

Exact traveling- wave solution for model geophysical systems

Exact traveling-wave solutions of time-dependent nonlinear inhomogeneous PDEs, describing several model systems in geophysical fluid dynamics, are found. The reduced nonlinear ODEs are treated as systems of linear algebraic equations in the derivatives. A variety of solutions are found, depending on the rank of the algebraic systems. The geophysical systems include acoustic gravity waves, inertial waves, and Rossby waves. The solutions describe waves which are, in general, either periodic or monoclinic. The present approach is compared with the earlier one due to Grundland (1974) for finding exact solutions of inhomogeneous systems of nonlinear PDEs.

Generation and scattering of sound in vortical flow

We present solutions to scattering problems for unsteady disturbances to a mean swirling flow in an annular duct with a rigid 'splitter'. This situation has application to rotor-stator interaction noise in aeroengines, where the flow downstream of the fan is swirling and bifurcates into the by-pass duct and the engine core. We also consider the trailing edge extension of this problem. Inviscid mean flow in a cylindrical annulus is considered, with both axial and swirling (azimuthal) velocity components. The presence of vorticity in the mean flow couples the acoustic and vorticity modes of irrotational flow. Instead we have one combined spectrum of acoustic-vorticity waves in which the 'sonic' and 'nearly-convected' modes are fully coupled. In addition to the aeroacoustics application the results offer insight into the behaviour of these acoustic-vorticity waves, and the precise nature of the coupling between the two types of mode. Two regimes are discussed in which progress has been made, one for a specialised mean flow, uniform axial flow and rigid body swirl, and a second regime in which the frequency is assumed large, valid for any axisymmetric mean flow. The Wiener-Hopf technique is used to solve the scattering problems mathematically, and we present numerical evaluations of these solutions. Several new effects are seen to arise due to the mean vorticity, in particular the generation of sound at a trailing edge due to the scattering of a nearly convected disturbance, in contrast to the way a convected gust silently passes a trailing edge in uniform mean flow.

Validity ranges of interfacial wave theories in a two-layer fluid system

In the present paper, we endeavor to accomplish a diagram, which demarcates the validity ranges for interfacial wave theories in a two-layer system, to meet the needs of design in ocean engineering. On the basis of the available solutions of periodic and solitary waves, we propose a guideline as principle to identify the validity regions of the interfacial wave theories in terms of wave period T, wave height H, upper layer thickness d(1), and lower layer thickness d(2), instead of only one parameter-water depth d as in the water surface wave circumstance. The diagram proposed here happens to be Le Mehautes plot for free surface waves if water depth ratio r = d(1)/d(2) approaches to infinity and the upper layer water density rho(1) to zero. On the contrary, the diagram for water surface waves can be used for two-layer interfacial waves if gravity acceleration g in it is replaced by the reduced gravity defined in this study under the condition of sigma = (rho(2) - rho(1))/rho(2) -> 1.0 and r > 1.0. In the end, several figures of the validity ranges for various interfacial wave theories in the two-layer fluid are given and compared with the results for surface waves.

非传播孤立波的数值模拟

非传播孤立波是近年来由中国学者发现的一种独特的孤立水波。本文通过数值求解非传播孤立波目前公认的控制方程-Miles导出的一个带共轭项的非线性立方Schrodinger方程，对非传播孤立波进行数值模拟。本文针对非传播孤立波的各种性质，作了大量的数值计算工作，并与实验观察的现象及人们对非传播孤立波的理论研究结果进行了比较和分析。为了得到稳定的非传播孤立波，本文讨论了Miles方程中的线性阻尼系数a的值，计算表明，线性阻尼a对能否形成稳定的非传播孤立波影响很大，在某些情况下，Laedke等人提出的Miles方程的非传播孤立波解的稳定性条件与我们对Miles方程的数值模拟的结果相当一致，a可在满足稳定性条件的区间内取值，但也发现在某些情况下Laedke等人的稳定性条件与我们的数值模拟不完全符合，证明Laedke等人关于非传播孤立波的稳定性条件只是一个必要条件，而不是充分条件。本文研究了两个非传播孤立波的相互作用，数值模拟表明，两个波的作用模式依赖于系统的参数，只有适当大小的外驱动频率和振幅及线性阻尼a可算出两个非传播孤立波周而复始的相互作用现象来，参数不合适时，两个波可能最终合并为一个非传播孤立波而不再分离，也可能彼此不发生作用，保持各自的独立。对不同的初始扰动及其演化的计算表明，要形成单个稳定的非传播孤立波，则初始扰动必须适当，否则扰动可能消失或发展成多个孤立波。关于形成非传播孤立波所需的外驱动条件，计算结果表明，只有适当大小的外驱动频率和振幅可形成稳定的非传播孤立波，数值结果可以描述驱动频率的上限和驱动振幅的上下限，但无法描述驱动频率的下限。我们的数值模拟工作说明Miles方程确实较好的描述了非传播孤立波的物理模型，该方程可以解释许多关于非传播孤立波的物理特性。但Miles方程无法对非传播孤立波的某些实验现象作出解释，因而有待于进一步研究改进。

Laser wakefield and self-modulation of driving pulse

A self-consistent theory of plasma response to a single laser beam is proposed. The driving pump is not viewed as invariant during its interaction with the plasmas. Its modulation by the plasmas has an obvious influence on the strength of the wakefield behind the pulse. This suggests that the compression of the low-intensity pulse by the plasmas might be a possible way to excite largae-amplitude wakefield. (C) 2003 American Institute of Physics.

Analysis and optimization of stress wave propagation in two-dimensional granular crystals with defects

Granular crystals are compact periodic assemblies of elastic particles in Hertzian contact whose dynamic response can be tuned from strongly nonlinear to linear by the addition of a static precompression force. This unique feature allows for a wide range of studies that include the investigation of new fundamental nonlinear phenomena in discrete systems such as solitary waves, shock waves, discrete breathers and other defect modes. In the absence of precompression, a particularly interesting property of these systems is their ability to support the formation and propagation of spatially localized soliton-like waves with highly tunable properties. The wealth of parameters one can modify (particle size, geometry and material properties, periodicity of the crystal, presence of a static force, type of excitation, etc.) makes them ideal candidates for the design of new materials for practical applications. This thesis describes several ways to optimally control and tailor the propagation of stress waves in granular crystals through the use of heterogeneities (interstitial defect particles and material heterogeneities) in otherwise perfectly ordered systems. We focus on uncompressed two-dimensional granular crystals with interstitial spherical intruders and composite hexagonal packings and study their dynamic response using a combination of experimental, numerical and analytical techniques. We first investigate the interaction of defect particles with a solitary wave and utilize this fundamental knowledge in the optimal design of novel composite wave guides, shock or vibration absorbers obtained using gradient-based optimization methods.

Wave uplift pressures on horizontal platforms

The major objective of the study has been to investigate in detail the rapidly-varying peak uplift pressure and the slowly-varying positive and negative uplift pressures that are known to be exerted by waves against the underside of a horizontal pier or platform located above the still water level, but not higher than the crests of the incident waves.

In a "two-dimensional" laboratory study conducted in a 100-ft long by 15-in.-wide by 2-ft-deep wave tank with a horizontal smooth bottom, individually generated solitary waves struck a rigid, fixed, horizontal platform extending the width of the tank. Pressure transducers were mounted flush with the smooth soffit, or underside, of the platform. The location of the transducers could be varied.

The problem of a d equate dynamic and spatial response of the transducers was investigated in detail. It was found that unless the radius of the sensitive area of a pressure transducer is smaller than about one-third of the characteristic width of the pressure distribution, the peak pressure and the rise-time will not be recorded accurately. A procedure was devised to correct peak pressures and rise-times for this transducer defect.

The hydrodynamics of the flow beneath the platform are described qualitatively by a si1nple analysis, which relates peak pressure and positive slowly-varying pressure to the celerity of the wave front propagating beneath the platform, and relates negative slowly-varying pressure to the process by which fluid recedes from the platform after the wave has passed. As the wave front propagates beneath the platform, its celerity increases to a maximum, then decreases. The peak pressure similarly increases with distance from the seaward edge of the platform, then decreases.

Measured peak pressure head, always found to be less than five times the incident wave height above still water level, is an order of magnitude less than reported shock pressures due to waves breaking against vertical walls; the product of peak pressure and rise-time, considered as peak impulse, is of the order of 20% of reported shock impulse due to waves breaking against vertical walls. The maximum measured slowly-varying uplift pressure head is approximately equal to the incident wave height less the soffit clearance above still water level. The normalized magnitude and duration of negative pressure appears to depend principally on the ratio of soffit clearance to still water depth and on the ratio of platform length to still water depth.

I. Quantum mechanics of one-dimensional two-particle models. II. A quantum mechanical treatment of inelastic collisions

Part I

Solutions of Schrödinger’s equation for system of two particles bound in various stationary one-dimensional potential wells and repelling each other with a Coulomb force are obtained by the method of finite differences. The general properties of such systems are worked out in detail for the case of two electrons in an infinite square well. For small well widths (1-10 a.u.) the energy levels lie above those of the noninteresting particle model by as much as a factor of 4, although excitation energies are only half again as great. The analytical form of the solutions is obtained and it is shown that every eigenstate is doubly degenerate due to the “pathological” nature of the one-dimensional Coulomb potential. This degeneracy is verified numerically by the finite-difference method. The properties of the square-well system are compared with those of the free-electron and hard-sphere models; perturbation and variational treatments are also carried out using the hard-sphere Hamiltonian as a zeroth-order approximation. The lowest several finite-difference eigenvalues converge from below with decreasing mesh size to energies below those of the “best” linear variational function consisting of hard-sphere eigenfunctions. The finite-difference solutions in general yield expectation values and matrix elements as accurate as those obtained using the “best” variational function.

The system of two electrons in a parabolic well is also treated by finite differences. In this system it is possible to separate the center-of-mass motion and hence to effect a considerable numerical simplification. It is shown that the pathological one-dimensional Coulomb potential gives rise to doubly degenerate eigenstates for the parabolic well in exactly the same manner as for the infinite square well.

Part II

A general method of treating inelastic collisions quantum mechanically is developed and applied to several one-dimensional models. The formalism is first developed for nonreactive “vibrational” excitations of a bound system by an incident free particle. It is then extended to treat simple exchange reactions of the form A + BC →AB + C. The method consists essentially of finding a set of linearly independent solutions of the Schrödinger equation such that each solution of the set satisfies a distinct, yet arbitrary boundary condition specified in the asymptotic region. These linearly independent solutions are then combined to form a total scattering wavefunction having the correct asymptotic form. The method of finite differences is used to determine the linearly independent functions.

The theory is applied to the impulsive collision of a free particle with a particle bound in (1) an infinite square well and (2) a parabolic well. Calculated transition probabilities agree well with previously obtained values.

Several models for the exchange reaction involving three identical particles are also treated: (1) infinite-square-well potential surface, in which all three particles interact as hard spheres and each two-particle subsystem (i.e. BC and AB) is bound by an attractive infinite-square-well potential; (2) truncated parabolic potential surface, in which the two-particle subsystems are bound by a harmonic oscillator potential which becomes infinite for interparticle separations greater than a certain value; (3) parabolic (untruncated) surface. Although there are no published values with which to compare our reaction probabilities, several independent checks on internal consistency indicate that the results are reliable.

ZnO-Based FBAR resonators with carbon nanotube electrodes

Film bulk acoustic resonator (FBAR) devices with carbon nanotube (CNT) electrodes directly grown on a ZnO film by thermal chemical vapor deposition have been fabricated. CNT electrodes possess a very low density and high acoustic impedance, which reduces the intrinsic mass loading effect resulting from the electrodes' weight and better confines the longitudinal acoustic standing waves inside the resonator, in turn providing a resonator with a higher quality factor. The influence of the CNTs on the frequency response of the FBAR devices was studied by comparing two identical sets of devices; one set comprised FBARs fabricated with chromium/ gold bilayer electrodes, and the second set comprised FBARs fabricated with CNT electrodes. It was found that the CNTs had a significant effect on attenuating traveling waves at the surface of the FBARs' membranes because of their high elastic stiffness. Three-dimensional finite element analysis of the devices fabricated was carried out, and the numerical simulations were consistent with the experimental results obtained. © 2011 IEEE.

Spin relaxation in diluted magnetic semiconductor quantum dots

Electron spin relaxation induced by phonon-mediated s-d exchange interaction in a II-VI diluted magnetic semiconductor quantum dot is investigated theoretically. The electron-acoustic phonon interaction due to piezoelectric coupling and deformation potential is included. The resulting spin lifetime is typically on the order of microseconds. The effectiveness of the phonon-mediated spin-flip mechanism increases with increasing Mn concentration, electron spin splitting, vertical confining strength, and lateral diameter, while it shows nonmonotonic dependence on the magnetic field and temperature. An interesting finding is that the spin relaxation in a small quantum dot is suppressed for strong magnetic field and low Mn concentration at low temperature.

Influence of the earth rotation on the interfacial wave solutions and wave-induced tangential stress in a two-layer fluid system

Interfacial waves and wave-induced tangential stress are studied for geostrophic small amplitude waves of two-layer fluid with a top free surface and a flat bottom. The solutions were deduced from the general form of linear fluid dynamic equations of two-layer fluid under the f-plane approximation, and wave-induced tangential stress were estimated based on the solutions obtained. As expected; the solutions derived from the present work include as special cases those obtained by Sun et al. (2004. Science in China, Set. D, 47(12): 1147-1154) for geostrophic small amplitude surface wave solutions and wave-induced tangential stress if tire density of the upper layer is much smaller than that of the lower layer. The results show that the interface and the surface will oscillate synchronously, and the influence of the earth's rotation both on the surface wave solutions and the interfacial wave solutions should be considered.

A SINGULAR EXACT SOLUTION FOR NONLINEAR SHALLOW-WATER ON A ROTATING EARTH

In this paper, we present an exact solution for nonlinear shallow water on a rotating planet. It is a kind of solitary waves with always negative wave height and a celerity smaller than linear shallow water propagation speed square-root gh. In fact, it propagates with a speed equal to (1 + a/h) square-root gh(1 + a/h) where a is the negative wave height. The lowest point of the water surface is a singular point where the first order derivative has a discontinuity of the first kind. The horizontal scale of the wave has actually no connection with the water depth.

南海西北部陆架海域内孤立波特征及机理研究

关于南海北部内孤立波的研究，现在是一个国际性研究热点，以往对南海北部海域的内孤立波的研究大都集中于南海东北部，即东沙-吕宋海峡海域。对于南海西北部文昌海域的内波现场调查研究几乎是空白。2005年4-10月中科院海洋所对南海西北部陆架海域进行了现场内波观测，获得了到目前为止国内连续观测时间最长、高分辨率、高质量的温度及流场数据。本文使用此次观测所获得的海流和温度资料，主要针对观测海域内孤立波特征及机理进行分析研究，取得了若干有重要科学意义的成果,主要为: 该海域是内孤立波多发地区，其中从2005年4月中旬到6月孤立波频繁出现且振幅较大，而6月中旬到9月中旬，内孤立波的发生频率明显下降，振幅也相对较小; 内孤立波的极性也表现出明显的季节性变化特征。研究发现内孤立波的季节性变化特征是与跃层的深浅和强弱密切相关的。 在2005年9月期间观测到了一系列的大振幅内孤立波，其中在同一测站的不同天内分别发现上凸型和下凹型内孤立波。研究表明这些内孤立波极有可能是由陆架坡折处的内潮因非线性和频散效应而局地产生的。这是首次通过现场观测确认南海西北部存在上凸型并且其为局地生成的内孤立波。 进一步分析发现在2005年8月21-23日，观测到了第二模态的内孤立波，这些内孤立波是与第二模态的内潮同步发生的，在连续两天内几乎相同的时刻分别观测到第二模态的内孤立波说明这些孤立波是潮致的。 在2005年4月22-28日发现长时间的强海流现象，强海流现象发生在当地的天文潮小潮期间，沿岸方向的流速明显大于垂直于岸方向的流速，通过分析表明强海流是由当地的内潮流引起的。 根据观测的温、流数据分析了内波场对台风的响应过程及内波谱特征，发现台风对观测站位的温度场和流场结构均有显著的影响。 这些在南海西北部的新发现和新认识对推动内孤立波的产生机制和应用技术的研究具有重要的学术价值。