Physical investigations of small particles : (I) aerosol particle charging and flux enhancement and (II) whispering gallery mode sensing

Part I

Particles are a key feature of planetary atmospheres. On Earth they represent the greatest source of uncertainty in the global energy budget. This uncertainty can be addressed by making more measurement, by improving the theoretical analysis of measurements, and by better modeling basic particle nucleation and initial particle growth within an atmosphere. This work will focus on the latter two methods of improvement.

Uncertainty in measurements is largely due to particle charging. Accurate descriptions of particle charging are challenging because one deals with particles in a gas as opposed to a vacuum, so different length scales come into play. Previous studies have considered the effects of transition between the continuum and kinetic regime and the effects of two and three body interactions within the kinetic regime. These studies, however, use questionable assumptions about the charging process which resulted in skewed observations, and bias in the proposed dynamics of aerosol particles. These assumptions affect both the ions and particles in the system. Ions are assumed to be point monopoles that have a single characteristic speed rather than follow a distribution. Particles are assumed to be perfect conductors that have up to five elementary charges on them. The effects of three body interaction, ion-molecule-particle, are also overestimated. By revising this theory so that the basic physical attributes of both ions and particles and their interactions are better represented, we are able to make more accurate predictions of particle charging in both the kinetic and continuum regimes.

The same revised theory that was used above to model ion charging can also be applied to the flux of neutral vapor phase molecules to a particle or initial cluster. Using these results we can model the vapor flux to a neutral or charged particle due to diffusion and electromagnetic interactions. In many classical theories currently applied to these models, the finite size of the molecule and the electromagnetic interaction between the molecule and particle, especially for the neutral particle case, are completely ignored, or, as is often the case for a permanent dipole vapor species, strongly underestimated. Comparing our model to these classical models we determine an “enhancement factor” to characterize how important the addition of these physical parameters and processes is to the understanding of particle nucleation and growth.

Part II

Whispering gallery mode (WGM) optical biosensors are capable of extraordinarily sensitive specific and non-specific detection of species suspended in a gas or fluid. Recent experimental results suggest that these devices may attain single-molecule sensitivity to protein solutions in the form of stepwise shifts in their resonance wavelength, \lambda_{R}, but present sensor models predict much smaller steps than were reported. This study examines the physical interaction between a WGM sensor and a molecule adsorbed to its surface, exploring assumptions made in previous efforts to model WGM sensor behavior, and describing computational schemes that model the experiments for which single protein sensitivity was reported. The resulting model is used to simulate sensor performance, within constraints imposed by the limited material property data. On this basis, we conclude that nonlinear optical effects would be needed to attain the reported sensitivity, and that, in the experiments for which extreme sensitivity was reported, a bound protein experiences optical energy fluxes too high for such effects to be ignored.

Methods for melting temperature calculation

Melting temperature calculation has important applications in the theoretical study of phase diagrams and computational materials screenings. In this thesis, we present two new methods, i.e., the improved Widom's particle insertion method and the small-cell coexistence method, which we developed in order to capture melting temperatures both accurately and quickly.

We propose a scheme that drastically improves the efficiency of Widom's particle insertion method by efficiently sampling cavities while calculating the integrals providing the chemical potentials of a physical system. This idea enables us to calculate chemical potentials of liquids directly from first-principles without the help of any reference system, which is necessary in the commonly used thermodynamic integration method. As an example, we apply our scheme, combined with the density functional formalism, to the calculation of the chemical potential of liquid copper. The calculated chemical potential is further used to locate the melting temperature. The calculated results closely agree with experiments.

We propose the small-cell coexistence method based on the statistical analysis of small-size coexistence MD simulations. It eliminates the risk of a metastable superheated solid in the fast-heating method, while also significantly reducing the computer cost relative to the traditional large-scale coexistence method. Using empirical potentials, we validate the method and systematically study the finite-size effect on the calculated melting points. The method converges to the exact result in the limit of a large system size. An accuracy within 100 K in melting temperature is usually achieved when the simulation contains more than 100 atoms. DFT examples of Tantalum, high-pressure Sodium, and ionic material NaCl are shown to demonstrate the accuracy and flexibility of the method in its practical applications. The method serves as a promising approach for large-scale automated material screening in which the melting temperature is a design criterion.

We present in detail two examples of refractory materials. First, we demonstrate how key material properties that provide guidance in the design of refractory materials can be accurately determined via ab initio thermodynamic calculations in conjunction with experimental techniques based on synchrotron X-ray diffraction and thermal analysis under laser-heated aerodynamic levitation. The properties considered include melting point, heat of fusion, heat capacity, thermal expansion coefficients, thermal stability, and sublattice disordering, as illustrated in a motivating example of lanthanum zirconate (La₂Zr₂O₇). The close agreement with experiment in the known but structurally complex compound La₂Zr₂O₇ provides good indication that the computation methods described can be used within a computational screening framework to identify novel refractory materials. Second, we report an extensive investigation into the melting temperatures of the Hf-C and Hf-Ta-C systems using ab initio calculations. With melting points above 4000 K, hafnium carbide (HfC) and tantalum carbide (TaC) are among the most refractory binary compounds known to date. Their mixture, with a general formula Ta_xHf_1-xC_y, is known to have a melting point of 4215 K at the composition Ta₄HfC₅, which has long been considered as the highest melting temperature for any solid. Very few measurements of melting point in tantalum and hafnium carbides have been documented, because of the obvious experimental difficulties at extreme temperatures. The investigation lets us identify three major chemical factors that contribute to the high melting temperatures. Based on these three factors, we propose and explore a new class of materials, which, according to our ab initio calculations, may possess even higher melting temperatures than Ta-Hf-C. This example also demonstrates the feasibility of materials screening and discovery via ab initio calculations for the optimization of "higher-level" properties whose determination requires extensive sampling of atomic configuration space.

Nonlinear Effects in Granular Crystals with Broken Periodicity

When studying physical systems, it is common to make approximations: the contact interaction is linear, the crystal is periodic, the variations occurs slowly, the mass of a particle is constant with velocity, or the position of a particle is exactly known are just a few examples. These approximations help us simplify complex systems to make them more comprehensible while still demonstrating interesting physics. But what happens when these assumptions break down? This question becomes particularly interesting in the materials science community in designing new materials structures with exotic properties In this thesis, we study the mechanical response and dynamics in granular crystals, in which the approximation of linearity and infinite size break down. The system is inherently finite, and contact interaction can be tuned to access different nonlinear regimes. When the assumptions of linearity and perfect periodicity are no longer valid, a host of interesting physical phenomena presents itself. The advantage of using a granular crystal is in its experimental feasibility and its similarity to many other materials systems. This allows us to both leverage past experience in the condensed matter physics and materials science communities while also presenting results with implications beyond the narrower granular physics community. In addition, we bring tools from the nonlinear systems community to study the dynamics in finite lattices, where there are inherently more degrees of freedom. This approach leads to the major contributions of this thesis in broken periodic systems. We demonstrate the first defect mode whose spatial profile can be tuned from highly localized to completely delocalized by simply tuning an external parameter. Using the sensitive dynamics near bifurcation points, we present a completely new approach to modifying the incremental stiffness of a lattice to arbitrary values. We show how using nonlinear defect modes, the incremental stiffness can be tuned to anywhere in the force-displacement relation. Other contributions include demonstrating nonlinear breakdown of mechanical filters as a result of finite size, and the presents of frequency attenuation bands in essentially nonlinear materials. We finish by presenting two new energy harvesting systems based on our experience with instabilities in weakly nonlinear systems.

超短脉冲激光光束被局域体全息光栅衍射的性质分析

利用二维耦合波理论,分析了超短脉冲激光光束被完全重叠型的局域体全息光栅衍射的时空变化性质,给出了衍射和透射脉冲激光光束沿光栅出射边界的强度时空分布。以LiNbO3晶体为例,数值研究了衍射光脉冲强度沿光栅出射边界的分布和脉冲波形的变化及光栅的总衍射效率受光栅二维尺寸、入射角度、光栅折射率调制度及入射脉冲的脉冲时域半峰全宽等条件的影响而变化的情况。与一维体全息光栅对超短脉冲激光光束衍射的性质,及此光栅对连续光衍射的性质作比较,给出了合理选择光栅参量及入射条件以在光栅出射边界上得到总衍射效率较大且分布较均匀的衍

Dualidade na teoria de Landau-Ginzburg da supercondutividade

Neste trabalho abordamos a teoria de Ginzburg-Landau da supercondutividade (teoria GL). Apresentamos suas origens, características e resultados mais importantes. A idéia fundamental desta teoria e descrever a transição de fase que sofrem alguns metais de uma fase normal para uma fase supercondutora. Durante uma transição de fase em supercondutores do tipo II é característico o surgimento de linhas de fluxo magnético em determinadas regiões de tamanho finito chamadas comumente de vórtices. A dinâmica destas estruturas topológicas é de grande interesse na comunidade científica atual e impulsiona incontáveis núcleos de pesquisa na área da supercondutividade. Baseado nisto estudamos como essas estruturas topológicas influenciam em uma transição de fase em um modelo bidimensional conhecido como modelo XY. No modelo XY vemos que os principais responsáveis pela transição de fase são os vórtices (na verdade pares de vórtice-antivórtice). Villain, observando este fato, percebeu que poderia tornar explícita a contribuição desses defeitos topológicos na função de partição do modelo XY realizando uma transformação de dualidade. Este modelo serve como inspiração para a proposta deste trabalho. Apresentamos aqui um modelo baseado em considerações físicas sobre sistemas de matéria condensada e ao mesmo tempo utilizamos um formalismo desenvolvido recentemente na referência [29] que possibilita tornar explícita a contribuição dos defeitos topológicos na ação original proposta em nossa teoria. Após isso analisamos alguns limites clássicos e finalmente realizamos as flutuações quânticas visando obter a expressão completa da função correlação dos vórtices o que pode ser muito útil em teorias de vórtices interagentes (dinâmica de vórtices).

有限尺寸平行电极的边缘电场效应

电场分布是影响集成电光器件特性的主要因素。本丈研究了有限尺寸平行电极的电场分布，得到了其电荷分布密度、电容、电场强度的数学解析式，并分析了边缘电场效应，在此基础上得到了在集成电光器件中相邻光通道互不干扰所需的平行电极对的间隔距离。最后以单晶1×4光开关为例给出了当电极板长度为5mm、宽度为2mm、电极板间距为2mm时，离开电极板边缘3mm处的电场强度就已经降到电极板中心处的5％左右，引起的信道串扰约为0．25％，可忽略不计。

展宽器元件失调及带通分析

通过光线追迹法给设计的反射式单光栅展宽器建立了一个数学计算模型。利用这个数学模型计算和分析了元件失调对反射式单光栅展宽器二阶色散量和输出光束发散角的影响，并考虑了反射式单光栅展宽器中衍射光栅和球形凹面镜的尺寸与展宽器带通的关系。发现当平面反射镜M1的纵向偏离角为0．2°时．展宽器的二阶色散量最大，偏离角大于或小于0．2°时，展宽器的二阶色散量随之减小；得到了元件失调会增加输出光束发散角的结论；并发现展宽器中衍射光栅和球形凹面镜尺寸的有限大小对带通有限制作用。提出了利用反射镜M1纵向的适当偏离增大展宽器二阶

Optimization of Pulse Temporal Contrast in Optical Parametric Chirped Pulse Amplification

In optical parametric chirped pulse amplification (OPCPA), the degradation of temporal contrast of the compressed signal pulse mainly results from spectral clipping in the grating stretcher with finite size of the optics, parametric fluorescence (PF) and the spectral variations transferred from temporal fluctuation of the pump pulse. The temporal contrast of the recompressed amplified pulse in the OPCPA system is studied numerically and a number of solutions are considered and optimized to achieve the highest temporal contrast.

Efficient decoy-state quantum key distribution with quantified security

We analyse the finite-size security of the efficient Bennett-Brassard 1984 protocol implemented with decoy states and apply the results to a gigahertz-clocked quantum key distribution system. Despite the enhanced security level, the obtained secure key rates are the highest reported so far at all fibre distances.

Graphene nanoribbon blends with P3HT for organic electronics.

In organic field-effect transistors (OFETs) the electrical characteristics of polymeric semiconducting materials suffer from the presence of structural/morphological defects and grain boundaries as well as amorphous domains within the film, hindering an efficient transport of charges. To improve the percolation of charges we blend a regioregular poly(3-hexylthiophene) (P3HT) with newly designed N = 18 armchair graphene nanoribbons (GNRs). The latter, prepared by a bottom-up solution synthesis, are expected to form solid aggregates which cannot be easily interfaced with metallic electrodes, limiting charge injection at metal-semiconductor interfaces, and are characterized by a finite size, thus by grain boundaries, which negatively affect the charge transport within the film. Both P3HT and GNRs are soluble/dispersible in organic solvents, enabling the use of a single step co-deposition process. The resulting OFETs show a three-fold increase in the charge carrier mobilities in blend films, when compared to pure P3HT devices. This behavior can be ascribed to GNRs, and aggregates thereof, facilitating the transport of the charges within the conduction channel by connecting the domains of the semiconductor film. The electronic characteristics of the devices such as the Ion/Ioff ratio are not affected by the addition of GNRs at different loads. Studies of the electrical characteristics under illumination for potential use of our blend films as organic phototransistors (OPTs) reveal a tunable photoresponse. Therefore, our strategy offers a new method towards the enhancement of the performance of OFETs, and holds potential for technological applications in (opto)electronics.

Electron tunneling through a planar single barrier in HgTe quantum wells with inverted band structures

We present a theoretical study on the electron tunneling through a single barrier created in a two-dimensional electron gas (2DEG) and quantum spin Hall (QSH) bar in a HgTe/CdTe quantum well with inverted band structures. For the 2DEG, the transmission shows the Fabry-Perot resonances for the interband tunneling process and is blocked when the incident energy lies in the bulk gap of the barrier region. For the QSH bar, the transmission gap is reduced to the edge gap caused by the finite size effect. Instead, transmission dips appear due to the interference between the edge states and the bound states originated from the bulk states. Such a Fano-like resonance leads to a sharp dip in the transmission which can be observed experimentally.

Lifetime distribution of spontaneous emission from line antennas in two-dimensional quasi-periodic photonic crystals

We investigate the lifetime distribution functions of spontaneous emission from line antennas embedded in finite-size two-dimensional 12-fold quasi-periodic photonic crystals. Our calculations indicate that two-dimensional quasi-periodic crystals lead to the coexistence of both accelerated and inhibited decay processes. The decay behaviors of line antennas are drastically changed as the locations of the antennas are varied from the center to the edge in quasi-periodic photonic crystals and the location of transition frequency is varied.

Geometrical learning, descriptive geometry, and biomimetic pattern recognition

Studies on learning problems from geometry perspective have attracted an ever increasing attention in machine learning, leaded by achievements on information geometry. This paper proposes a different geometrical learning from the perspective of high-dimensional descriptive geometry. Geometrical properties of high-dimensional structures underlying a set of samples are learned via successive projections from the higher dimension to the lower dimension until two-dimensional Euclidean plane, under guidance of the established properties and theorems in high-dimensional descriptive geometry. Specifically, we introduce a hyper sausage like geometry shape for learning samples and provides a geometrical learning algorithm for specifying the hyper sausage shapes, which is then applied to biomimetic pattern recognition. Experimental results are presented to show that the proposed approach outperforms three types of support vector machines with either a three degree polynomial kernel or a radial basis function kernel, especially in the cases of high-dimensional samples of a finite size. (c) 2005 Elsevier B.V. All rights reserved.

Kinetic study for hopping conduction through deoxyribonucleic acid molecules

Recent experiments indicated that disorder effect in deoxyribonucleic acid (DNA) may lead to a transition of the electronic hole transport mechanism from band resonant tunneling to thermally activated hopping. In this letter, based on Mott's variable-range hopping theory, we present a kinetic study for the hole transport properties of DNA molecules. Beyond the conventional argument in large-scale systems, our numerical study for finite-size DNA molecules reveals a number of unique features for: (i) the current-voltage characteristics, (ii) the temperature and length dependence, and (iii) the transition from conducting to insulating behaviors. (c) 2005 American Institute of Physics.

A speaker-independent continuous speech recognition system using biomimetic pattern recognition

In speaker-independent speech recognition, the disadvantage of the most diffused technology (HMMs, or Hidden Markov models) is not only the need of many more training samples, but also long train time requirement. This paper describes the use of Biomimetic pattern recognition (BPR) in recognizing some mandarin continuous speech in a speaker-independent manner. A speech database was developed for the course of study. The vocabulary of the database consists of 15 Chinese dish's names, the length of each name is 4 Chinese words. Neural networks (NNs) based on Multi-weight neuron (MWN) model are used to train and recognize the speech sounds. The number of MWN was investigated to achieve the optimal performance of the NNs-based BPR. This system, which is based on BPR and can carry out real time recognition reaches a recognition rate of 98.14% for the first option and 99.81% for the first two options to the persons from different provinces of China speaking common Chinese speech. Experiments were also carried on to evaluate Continuous density hidden Markov models (CDHMM), Dynamic time warping (DTW) and BPR for speech recognition. The Experiment results show that BPR outperforms CDHMM and DTW especially in the cases of samples of a finite size.