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Quadratic Nonlinearity In Covalently And Non-Covalently Linked Molecules In SolutionBhattacharya, Mily 06 1900 (has links)
This thesis deals with the investigation of the first hyperpolarizabilities (β) of a large number of molecules linked to other molecules either covalently or noncovalently. Chapter 1 gives a brief
introduction to supramolecular chemistry and Nonlinear Optics (NLO). A survey of literature pertinent to noncovalently interacting supramolecular assembly and their NLO properties as well as NLO properties of oligomeric systems has been presented. The scope of the present
investigation has been described at the end of the chapter.
Chapter 2 discusses all the methods used in carrying out this thesis work. The first
hyperpolarizabilities (β) of all the compounds have been measured by the hyper Rayleigh scattering (HRS) technique; the experimental details of which are written in this chapter. Various spectroscopic techniques such as NMR, IR, UV-Vis, etc. that were used in the investigation have been presented.
The subsequent chapters 3-5 deal with the actual results obtained in this work. In chapter 3 first hyperpolarizabilities of o-, m-, and p-aminobenzoic acids and their oligomers viz., dimer, trimer and tetramer (covalently linked) have been studied. The compounds are synthesized and characterized by various spectroscopic methods and their β values have been measured by HRS. The hyperpolarizability increases in going from the monomer to the dimer but decreases
subsequently from the dimer to the trimer to the tetramer. This unexpected trend in β has been attributed to the formation of molecular aggregates in the trimers and tetramers. Further evidences of aggregation come from the results of1H NMR spectroscopy and conductivity measurements.
In chapter 4, synthesis, characterization and HRS investigation to probe the formation,
dissociation and binding constants of hydrogen bonded supramolecular complexes (noncovalent interaction) formed in solution between 6-amino-2-(pivaloylamino)pyridine and ferrocene functionalized barbituric acid
and 5-methoxy-N,N′-bis(6-amino-2-pyridinyl)-1,3-benzenedicarboxamide and ferrocenyl barbituric acid have been described. From the HRS data the stoichiometry of the supramolecular complexes has been determined and compared to that from the NMR data. Some of the complex stoichiometries that are measured by HRS have not been seen in the NMR data and vice versa. The results have been rationalized in terms of the strengths and weaknesses of various spectroscopic methods as applied to this problem. Many
fold increase in the β value has been realized in the supramolecular complex formation process.
Depolarized HRS experiments have been carried out to obtain structural information on the complexes.
In the last chapter the synthesis, characterization and measurements on the first hyperpolarizabilities of unsubstituted tetraphenylporphyrin and its metallated complexes have been presented. Synthesis of supramolecular complexes of ferrocenyl barbituric acid with functionalized porphyrin compounds has been carried out although the amount of the final complex was insufficient for HRS measurements. This chapter ends with a perspective for the
future work in the direction.
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Biomechanically informed nonlinear speech signal processingLittle, M. A. January 2007 (has links)
Linear digital signal processing based around linear, time-invariant systems theory finds substantial application in speech processing. The linear acoustic source-filter theory of speech production provides ready biomechanical justification for using linear techniques. Nonetheless, biomechanical studies surveyed in this thesis display significant nonlinearity and non-Gaussinity, casting doubt on the linear model of speech production. In order therefore to test the appropriateness of linear systems assumptions for speech production, surrogate data techniques can be used. This study uncovers systematic flaws in the design and use of exiting surrogate data techniques, and, by making novel improvements, develops a more reliable technique. Collating the largest set of speech signals to-date compatible with this new technique, this study next demonstrates that the linear assumptions are not appropriate for all speech signals. Detailed analysis shows that while vowel production from healthy subjects cannot be explained within the linear assumptions, consonants can. Linear assumptions also fail for most vowel production by pathological subjects with voice disorders. Combining this new empirical evidence with information from biomechanical studies concludes that the most parsimonious model for speech production, explaining all these findings in one unified set of mathematical assumptions, is a stochastic nonlinear, non-Gaussian model, which subsumes both Gaussian linear and deterministic nonlinear models. As a case study, to demonstrate the engineering value of nonlinear signal processing techniques based upon the proposed biomechanically-informed, unified model, the study investigates the biomedical engineering application of disordered voice measurement. A new state space recurrence measure is devised and combined with an existing measure of the fractal scaling properties of stochastic signals. Using a simple pattern classifier these two measures outperform all combinations of linear methods for the detection of voice disorders on a large database of pathological and healthy vowels, making explicit the effectiveness of such biomechanically-informed, nonlinear signal processing techniques.
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Wavelength Conversion in Domain-disordered Quasi-phase Matching Superlattice WaveguidesWagner, Sean 31 August 2011 (has links)
This thesis examines second-order optical nonlinear wave mixing processes in domain-disordered quasi-phase matching waveguides and evaluates their potential use in compact, monolithically integrated wavelength conversion devices. The devices are based on a GaAs/AlGaAs superlattice-core waveguide structure with an improved design over previous generations. Quantum-well intermixing by ion-implantation is used to create the quasi-phase matching gratings in which the nonlinear susceptibility is periodically suppressed.
Photoluminescence experiments showed a large band gap energy blue shift around 70 nm after intermixing. Measured two-photon absorption coefficients showed a significant polarization dependence and suppression of up to 80% after intermixing. Similar polarization dependencies and suppression were observed in three-photon absorption and nonlinear refraction. Advanced modeling of second-harmonic generation showed reductions of over 50% in efficiency due to linear losses alone. Self-phase modulation was found to be the dominant parasitic nonlinear effect on the conversion efficiency, with reductions of over 60%. Simulations of group velocity mismatch showed modest reductions in efficiency of less than 10%.
Experiments on second-harmonic generation showed improvements in efficiency over previous generations due to low linear loss and improved intermixing. The improvements permitted demonstration of continuous wave second-harmonic generation for the first time in such structures with output power exceeding 1 µW. Also, Type-II phase matching was demonstrated for the first time. Saturation was observed as the power was increased, which, as predicted, was the result of self-phase modulation when using 2 ps pulses. By using 20 ps pulses instead, saturation effects were avoided. Thermo-optically induced bistability was observed in continuous wave experiments.
Difference frequency generation was demonstrated with wavelengths from the optical C-band being converted to the L- and U-bands with continuous waves. Conversion for Type-I phase matching was demonstrated over 20 nm with signal and idler wavelengths being separated by over 100 nm. Type-II phase matched conversion was also observed. Using the experimental data for analysis, self-pumped conversion devices were found to require external amplification to reach practical output powers. Threshold pump powers for optical parametric oscillators were calculated to be impractically large. Proposed improvements to the device design are predicted to allow more practical operation of integrated conversion devices based on quasi-phase matching superlattice waveguides.
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Nonlinearity Preserving Post-transformationsSertkaya, Isa 01 June 2004 (has links) (PDF)
Boolean functions are accepted to be cryptographically strong if they satisfy some
common pre-determined criteria. It is expected that any design criteria should remain invariant under
a large group of transformations due to the theory of similarity of secrecy
systems proposed by Shannon. One of the most important design criteria for
cryptographically strong Boolean functions is the nonlinearity criterion. Meier and
Staffelbach studied nonlinearity preserving transformations,
by considering the invertible transformations acting on the arguments of
Boolean functions, namely the pre-transformations. In this thesis, first, the
results obtained by Meier and Staffelbach are presented. Then, the invertible
transformations acting on the truth tables of Boolean functions, namely the post-transformations,
are studied in order to determine whether they keep the nonlinearity
criterion invariant. The equivalent counterparts of Meier and Staffelbach&rsquo / s
results are obtained in terms of the post-transformations. In addition, the existence
of nonlinearity preserving post-transformations, which are not equivalent
to pre-transformations, is proved. The necessary and sufficient conditions for an
affine post-transformation to preserve nonlinearity are proposed and proved. Moreover, the sufficient conditions
for an non-affine post-transformation to keep nonlinearity invariant are proposed. Furthermore,
it is proved that the smart hill climbing method, which is introduced to
improve nonlinearity of Boolean functions by Millan et. al., is equivalent to applying
a post-transformation to a single Boolean function. Finally, the necessary and
sufficient condition for an affine pre-transformation to preserve the strict avalanche
criterion is proposed and proved.
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Divisibility Properties On Boolean Functions Using The Numerical Normal FormGologlu, Faruk 01 September 2004 (has links) (PDF)
A Boolean function can be represented in several different forms. These different
representation have advantages and disadvantages of their own. The Algebraic Normal
Form, truth table, and Walsh spectrum representations are widely studied in
literature. In 1999, Claude Carlet and Phillippe Guillot introduced the Numerical
Normal Form. NumericalNormal Form(NNF) of a Boolean function is similar to Algebraic
Normal Form, with integer coefficients instead of coefficients from the two
element field. Using NNF representation, just like the Walsh spectrum, characterization
of several cryptographically important functions, such as resilient and bent
functions, is possible. In 2002, Carlet had shown several divisibility results concerning
resilient and correlation-immune functions using NNF. With these divisibility
results, Carlet is able to give bounds concerning nonlinearity of resilient and correlation
immune functions.
In this thesis, following Carlet and Guillot, we introduce the Numerical Normal
Form and derive the pairwise relations between the mentioned representations.
Characterization of Boolean, resilient and bent functions using NNF is also given.
We then review the divisibility results of Carlet, which will be linked to some results
on the nonlinearity of resilient and correlation immune functions.
We show the Mö / bius inversion properties of NNF of a Boolean function, using
Gian-Carlo Rota&rsquo / s work as a guide. Finally, using a lot of the mentioned results, we prove a necessary condition on theWalsh spectrum of Boolean functions with given
degree.
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Constructions Of Bent FunctionsSulak, Fatih 01 January 2006 (has links) (PDF)
In cryptography especially in block cipher design, Boolean functions are the
basic elements. A cryptographic function should have high nonlinearity as it can
be attacked by linear attack.
In this thesis the highest possible nonlinear boolean functions in the even
dimension, that is bent functions, basic properties and construction methods of
bent functions are studied. Also normal bent functions and generalized bent
functions are presented.
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Nonlinear acoustic echo cancellationShi, Kun 10 November 2008 (has links)
The objective of this research is to presents new acoustic echo cancellation design methods that can effectively work in the nonlinear environment. Acoustic echo is an annoying issue for voice communication systems. Because of room acoustics and delay in the transmission path, echoes affect the sound quality and may hamper communications. Acoustic echo cancellers (AECs) are employed to remove the acoustic echo while keeping full-duplex communications. AEC designs face a variety of challenges, including long room impulse response, acoustic path nonlinearity, ambient noise, and double-talk situation. We investigate two parts of echo canceller design: echo cancellation algorithm design and control logic algorithm design. In the first part, our work focuses on the nonlinear adaptive and fast-convergence algorithms. We investigate three different structures: predistortion linearization, cascade structure, and nonlinear residual echo suppressor. Specifically, we are interested in the coherence function, since it provides a means for quantifying linear association between two stationary random processes. By using the coherence as a criterion to design the nonlinear echo canceller in the system, our method guarantees the algorithm stability and leads to a faster convergence rate. In the second part, our work focuses on the robustness of AECs in the presence of interference. With regard to the near-end speech, we investigate the double-talk detector (DTD) design in conjunction with nonlinear AECs. Specifically, we propose to design a DTD based on the mutual information (MI). We show that the advantage of the MI-based method, when compared with the existing methods, is that it is applicable to both the linear and nonlinear scenarios. With respect to the background noise, we propose a variable step-size and variable tap-length least mean square (LMS) algorithm. Based on the fact that the room impulse response usually exhibits an exponential decay power profile in acoustic echo cancellation applications, the proposed method finds optimal step size and tap length at each iteration. Thus, it achieves faster convergence rate and better steady-state performance. We show a number of experimental results to illustrate the performance of the proposed algorithms.
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Optimisation Heuristics for CryptologyClark, Andrew J. January 1998 (has links)
The aim of the research presented in this thesis is to investigate the use of various optimisation heuristics in the fields of automated cryptanalysis and automated cryptographic function generation. These techniques were found to provide a successful method of automated cryptanalysis of a variety of the classical ciphers. Also, they were found to enhance existing fast correlation attacks on certain stream ciphers. A previously proposed attack of the knapsack cipher is shown to be flawed due to the absence of a suitable solution evaluation mechanism. Finally, a new approach for finding highly nonlinear Boolean functions is introduced.
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Éléments finis spéciaux pour l’analyse linéaire et non-linéaire géométrique des structures composites à renforts fibreux / Special finite elements for linear and geometricaly non linear analysis of fiber reinforced composite structuresTiar, Mohamed Amine 29 March 2017 (has links)
La modélisation numérique des structures composites à renfort fibreux de géométrie complexe constitue un axe de recherche majeur afin de prédire correctement leur comportement mécanique. Dans ce contexte, l’étude menée dans ce travail de thèse porte sur le développement de nouveaux éléments finis basés sur une approche numérique multi-échelle, appelée Approche de la Fibre Projetée (AFP). Cette approche a l’avantage de tenir compte de la présence des fibres au sein d’un espace matrice sans les discrétiser, ce qui limite considérablement la taille du système à résoudre. Pour analyser le comportement des structures composites, plusieurs éléments finis 2D et 3D ont été développés et implémentés dans le code ABAQUS via la routine UEL. Plusieurs cas tests de validation sont considérés pour tester la précision et l’efficacité des éléments finis proposés et les résultats obtenus sont globalement en bon accord avec les solutions de référence. De plus, l’intérêt de la nouvelle approche (AFP) est particulièrement mis en exergue en étudiant des structures composites complexe à renfort 3D : une plaque sandwich cousue et une plaque sandwich à âme creuse renforcée par des fibres en forme de « 8 ». / Numerical modeling of composite materials and structures with complex geometry of fiber reinforcement, such as stitched composites, constitutes a major research axis in order to correctly predict their mechanical behavior. Within this context, this study focuses on the development of new linear and nonlinear specific finite elements based on a multiscale numerical approach, called the Projected Fiber Approach (PFA). This numerical approach has the advantage of taking into account the presence of fi bers, long or short and distributed randomly or specifically, within a matrix space without discretizing them. Consequently, the obtained system of equations size is equivalent to that without reinforcement (matrix), which considerably reduces the computational cost. To analyze the linear and geometrically nonlinear behaviors of composite structures, two membrane finite elements, named PFT3 and PFQ4, and a 3D solid finite element, named PFH8, were developed and implemented into the commercial finite element code ABAQUS via the user element subroutine (UEL). Several numerical linear and nonlinear tests are considered to assess the accuracy and efficiency of the proposed composite finite elements, and the obtained results are globally in good agreement with the reference solutions. Moreover, the major interest of the PFA approach is particularly emphasized by studying two 3D complex reinforced composite structures: a stitched sandwich plate and a hollow core sandwich plate reinforced by "8" shape fibers.
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[en] GRAPHICS INTERACTIVE TOOL FOR THE DESIGN OF REINFORCED CONCRETE PLANE FRAMES CONSIDERING GEOMETRIC NONLINEARITY / [pt] FERRAMENTA GRÁFICO-INTERATIVA PARA O DIMENSIONAMENTO DE PÓRTICOS PLANOS DE CONCRETO ARMADO CONSIDERANDO NÃO LINEARIDADE GEOMÉTRICAMARIA FLAVIA DUTRA SILVA SILVA 30 August 2017 (has links)
[pt] O objetivo deste trabalho é complementar a ferramenta de dimensionamento de pórticos planos de concreto armado já existente no Ftool, programa educacional amplamente difundido no meio acadêmico. Para tanto, foi introduzido o cálculo e dimensionamento de pilares de concreto armado à flexão composta reta. Foi adicionada uma nova seção transversal, referente aos pilares retangulares com armaduras simétricas. Além disso, foi necessária a inclusão de um método de análise não linear geométrica simplificado que fosse compatível com a filosofia do Ftool, aliando simplicidade e eficiência: o método dos Dois Ciclos Iterativos. A ferramenta para análise não linear geométrica pode ou não ser utilizada em
conjunto com a ferramenta para o dimensionamento de estruturas de concreto armado, sendo possível a análise não linear geométrica de pórticos planos constituídos de outros materiais. A metodologia utilizada para o dimensionamento dos pilares em concreto armado é a que se baseia nas zonas de solicitação e foi
adequada para estar de acordo com a norma brasileira vigente, a ABNT NBR 6118:2014, assim como o dimensionamento de vigas existente em uma versão anterior dessa ferramenta. Dessa forma, é possível exibir resultados para pórticos planos compostos por vigas e pilares em concreto armado, nos mesmos moldes da versão anterior, com diagramas para as armaduras longitudinal e transversal disponíveis nos modos necessária e adotada. / [en] The main objective of this work is to complement the reinforced concrete plane frames design tool already existing in Ftool, an educational tool widely known in academia. Therefore, the design of reinforced concrete columns was introduced. A new cross section for rectangular columns with symmetrical steel
reinforcement was added. In addition to that, the inclusion of a simplified nonlinear geometric analysis that was in accordance to the philosophy of Ftool, combining simplicity and efficiency, was needed: the Two cycles iterative method. The nonlinear geometric analysis tool may or may not be used together with the reinforced concrete plane frames design tool, thus allowing for geometric nonlinear analyses of plane frames of other materials. The methodology used for the reinforced concrete frames design was based on solicitation zones and was adapted to be in accordance with the Brazilian code, the ABNT NBR
6118:2014, as was the existing reinforced concrete beams design tool. It is now possible to show results for plane frames composed of reinforced concrete columns and beams just as in the previous version of the reinforced concrete design tool, showing diagrams for the necessary and adopted longitudinal and transversal steel reinforcement.
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