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Density Functional Theory and Accelerated Dynamics Studies of the Structural andNon-equilibrium Properties of Bulk Alloys and Thin-FilmsKhatri, Indiras 11 July 2022 (has links)
No description available.
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Light Scattering Studies of Dynamics of Bent-Core Liquid CrystalsStojadinovic, Strahinja 08 February 2005 (has links)
No description available.
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Liquid-Crystalline Ordering in Semiflexible Polymer Melts and Blends: A Monte Carlo Simulation StudyKhanal, Kiran 26 August 2013 (has links)
No description available.
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Integration magnetresonanztomographischer und computertomographischer Daten mit isotropen Voxeln in die Protonenbestrahlungsplanung bei okularen TumorenLemke, Arne-Jörn 12 November 2001 (has links)
Die Bestrahlungstherapie von Aderhautmelanomen mit der Protonentherapie stellt ein sehr präzises Behandlungsverfahren dar, welches hohe Ansprüche an die zugrundliegende Bildgebung stellt. Die Magnetresonanztomographie (MRT) und Computertomographie (CT) scheinen prinzipiell in der Lage, mit geeigneten Oberflächenspulen bzw. angepaßter Untersuchungstechnik diese Ansprüche zu erfüllen. Ziel der Arbeit ist die Bereitstellung und Überprüfung eines bildgebenden Systems, das einerseits die diagnostischen und differentialdiagnostischen Aufgaben für die Differenzierung und das Staging von Aderhautmelanomen erfüllt und andererseits als Grundlage der Bestrahlungsplanung dienen kann. Erstrebenswert ist dabei die Erstellung von Schnittbildern bestehend aus isotropen Voxeln, d.h. Voxeln mit identischer Kantenlänge, mit der Magnetresonanztomographie (MRT) und der Computertomographie (CT). Zur Differenzierung der unterschiedlichen Tumorentitäten wurden verschiedene Untersuchungen mit zum Teil großen Patientenkollektiven durchgeführt und histologisch und klinisch korreliert bzw. verifiziert. Dabei konnte das MR-morphologische Erscheinungsbild der relevanten Erkrankungen studiert werden. Die Genauigkeit der MR-gestützten Tumorvolumetrie wurde in vitro im Tierversuch und in vivo am Patientenauge überprüft. Zur Überprüfung der Genauigkeit der MR-Bildgebung mit isotropen Voxeln wurden unterschiedliche Spulen getestet und verschiedene Phantomuntersuchungen durchgeführt. Entsprechend wurde auch die CT evaluiert. Mit der digitalen Bildfusion wurden die MRT- und die CT-Daten in einen gemeinsamen Datensatz überführt, der sowohl zur Bestimmung der Genauigkeit beider Verfashren als auch als Basis zur Bestrahlungsplanung verwendet werden konnte. Mit einer optimierten Untersuchungstechnik konnten Schnittbilder auf der Basis von CT und MRT zur Verfügung gestellt werden, die eine präzise Planung der Protonenbestrahlung beim Aderhautmelanom ermöglichen. / The radiation therapy of uveal melanomas using proton therapy is a very precise therapy procedure, that makes high demands on the underlying imaging modalities. In general magnetic resonance imaging (MRI) and computed tomography (CT) have the potential to fulfill these criteria using suited surface coils and optimized imaging techniques, respectively. Purpose of the investigations was the preparation and evaluation of an imaging system, that allows diagnosis and differetial diagnosis of uveal melanomas including staging on the one hand. On the other hand it should be the base for high precision radiation therapy planning. The preparation of images with isotropic voxels, i.e. the edges of the voxels have identical size, is desirable with both magnetic resonance imaging (MRI) and computed tomography (CT). Several examinations on large patient groups were performed for the differentiation of different tumor entities and compared with clinical and histopathological outcome. The precision of the MR-based tumor volumetry was evaluated with animal studies in vitro and patient eyes in vivo. The MR-imaging with isotropic voxels was evaluated using several surface coils and phantom examinations. Comparable examinations were performed regarding CT. Digital image fusion of CT and MRI data sets was used to evaluate the precision of both modalities and for planning of radiation therapy. Using optimized examination techniques both CT and especially MRI are suitable for a precise proton therapy planning of uveal melanoma.
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Développement d’une approche quantitative pour l’étude du poumon équin : fixation et échantillonnage pour l’application des principes de la stéréologieGélinas-Lymburner, Emilie 03 1900 (has links)
La présente étude visait à développer un protocole de fixation et d'échantillonnage pour le poumon équin suivant les directives publiées sur l’utilisation d’une approche stéréologique de type « design-based ».
Les poumons gauches de chevaux contrôles et atteints du souffle ont été fixés avec du formaldéhyde 10% pendant 48h à une pression constante de 25-30 cm d’H2O. Les poumons ont été sectionnés en 20-21 tranches d’une épaisseur d'environ 2,5 cm chacune; de 10-11 tranches ont été sélectionnées de façon aléatoire et systématique pour la mesure du volume de référence avec la méthode de Cavalieri. Un protocole d’échantillonnage systématique, aléatoire et uniforme utilisant le principe du « smooth fractionator » et un poinçon à biopsie de 17 mm ont été utilisés pour échantillonner une fraction représentative de chaque poumon. Les méthodes d’échantillonnage de sections verticales, uniformes et aléatoires (VUR) et d’échantillonnage isotropique, uniforme et aléatoire (IUR) ont toutes deux été effectuées pour comparer le nombre de voies respiratoires en coupe perpendiculaire obtenues à partir de chaque méthode. L'architecture globale et la qualité des tissus fixés ont également été évaluées.
Des spécimens pulmonaires équins ont été échantillonnés avec succès selon un protocole visant à produire des données morphométriques valides. Les tissus ont été fixés avec un minimum d'artéfacts et contenaient une quantité suffisante de voies respiratoires en coupe perpendiculaire dans les deux types d’échantillons.
En conclusion, un protocole de fixation et d'échantillonnage adapté au poumon équin permettant l'utilisation d'une approche stéréologique de type « design-based » a été élaboré pour l’étude du remodelage des voies respiratoires. / The present study aimed at developing a fixation and sampling protocol for the horse lung in agreement with recent published guidelines for a design-based stereology approach.
The left lungs from control and from heaves-affected horses were fixed in 10% formaldehyde for 48hr at a controlled constant pressure of 25-30 cm H2O. Lungs were cut into 20-21 slices of a thickness of approximately 2.5cm each; 10-11 slices were then randomly and systematically selected for the measurement of the reference volume using the Cavalieri method. A systematic, uniform and random sampling (SURS) protocol using a 17 mm punch biopsy and the smooth fractionator principle was used to select a representative fraction of each lung. The vertical uniform random (VUR) and isotropic uniform random (IUR) sampling methods were both performed to compare the number of perpendicular airways obtained with each method. The general architecture and the quality of the fixed tissues were also evaluated.
Equine lung tissues were successfully sampled with a protocol designed to yield accurate morphometric data. The tissues were fixed with minimal artifacts and contained an adequate amount of perpendicular airways in both VUR and IUR sections.
In conclusion, we developed a fixation and sampling protocol adapted to the equine lung allowing the use of a design-based stereology approach to study airway remodeling.
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Contribution à la compréhension de la fonctionnalisation mécanique de surface des composites à matrice thermoplastique (PEEK) destinés à l'assemblage par collageOurahmoune, Reda El Hak 20 December 2012 (has links)
L’assemblage des matériaux composites thermoplastiques tel que le PEEK est l’une des problématiques majeure de l’industrie aéronautique. Actuellement, différentes techniques sont développées pour assurer l’assemblage structural de ces matériaux, tels que : le soudage, le rivetage, le boulonnage et le collage. Les enjeux industriels majeurs sont principalement, à l’heure actuelle, la conception des structures simplifiées au maximum afin de réduire les coûts de production et la réduction des consommations énergétiques. A cet effet, l’industrie aéronautique fait fréquemment appel à l’assemblage par collage en raison de nombreux avantages qu’il offre (gain de poids, distribution régulière des contraintes, absence de trous) par rapport aux autres techniques existantes. Le PEEK (PolyEtherEtherKetone), est un matériau polymère semi-cristallin thermoplastique, à hautes performances. Ce matériau est souvent utilise dans l’industrie aéronautique principalement renforce par des fibres de carbone ou de verre. Cependant, du fait du niveau élevé de sa résistance chimique l’assemblage par collage du PEEK et de ses composites nécessitent des traitements de surfaces appropries et optimises. Or, afin d’obtenir un system collé à haute performance, la problématique scientifique et technique doit être concentrée sur la jonction entre les éléments à assembler. En effet, la qualité de cette jonction est de la plus haute importance car elle doit permettre un transfert optimal des contraintes thermomécaniques lorsque l’assemblage est soumis a ses conditions d'usage. Cette étude concerne donc, l’amélioration des propriétés mécaniques (monotones et cycliques) de l’assemblage par collage PEEK/PEEK. Dans cette optique, un traitement de surface simple de mise en œuvre est proposé. Ce traitement est le sablage, qui permet la modification topographique (morphologique) de surface. La compréhension des différents phénomènes d’interaction aux interfaces intervenant dans l’amélioration du comportement mécanique du joint de colle et qui s’inscrit dans la triptyque : « Rhéologie, Physico-chimie et topographie », est l’enjeu scientifique majeur dans cette thèse. Dans un premier temps, l’influence des paramètres du traitement tels que le temps de projection, la taille des particules, sur la morphologie de surface de différents matériaux à base de PEEK a été analysée, permettant ainsi d’établir la corrélation entre les paramètres morphologiques et les mécanismes de modification topographique de surface intervenant pendant le traitement de surface. L’un des facteurs clefs pour la compréhension des mécanismes d’interaction entre l’adhésif liquide et le substrat solide est la mouillabilité. L’analyse du comportement au mouillage en fonction des différents paramètres du traitement a été réalisée. La mouillabilité des surfaces traitées est fortement affectée par la rugosité de surface créée après ce traitement. La relation entre les paramètres morphologiques et la mouillabilité a été discutée. Enfin, l’influence des paramètres du traitement par sablage sur le comportement mécanique monotone et à long terme (essais de fatigue) sur la résistance du joint colle a été étudié à l’aide d’essais de cisaillement sur éprouvettes à simple recouvrement. Ceci a conduit, à la proposition de paramètres morphologiques surfaciques spécifiques pour l’optimisation du comportement mécanique du joint de colle des matériaux composites à matrice PEEK. / One of most problematic in the aeronautical industries is the structural joining of the high performance thermoplastic composites like PEEK composites. Actually, a lot of technologies are used for joining thermoplastic composites like welding, bolting, riveting, fastening and adhesive bonding. Due to the various advantages that characterize the adhesive bonding method, such an uniform stress distribution along the joint, weight‐light and cost reduction, makes this technique more desirable to join thermoplastic composites materials compared to the other joining techniques. PEEK (PolyEtherEtherKetone) is a semi‐crystalline thermoplastic material with high performance. This material is wildly used in aeronautical industries, principally, reinforced with carbon of glass fibres. However, its high chemical resistance makes the adhesive bonding of PEEK and its composites difficult and therefore an appropriate and optimised surface treatment is necessary. In the aim to obtain a bonded system with high performance, scientific and technical problematic should be focussed on the junction between adherents. Indeed, the quality of this junction is of utmost importance because it must allow optimum transfer of thermomechanical stresses when the assembly is subject to its terms of use. Though, at this time it is well known that thermoplastic composite materials are difficult to bond with‐out surface treatment. This study, therefore, relates to the improvement of mechanical properties (monotonic and cyclic) of the adhesive bonding system PEEK / PEEK. In this context, a surface treatment, easy to implement, is proposed. This surface treatment is sandblasting, which enables surface topographic (morphological) modifications. Understanding of various phenomena of interfaces interaction involved in the improvement of the mechanical behavior of the adhesive joint and is part of the triptych "Rheology, Physico‐chemistry and topography" is the major scientific challenge in this thesis. Initially, the influence of processing parameters such as the projection time, the particle size on surface morphology of various materials based on PEEK was analysed, thus allowing establishing the correlation between morphological parameters and modification mechanisms involved during surface treatment surface. One of the key factors for understanding the mechanisms of interaction between the liquid adhesive and the solid substrate is wettability. The analysis of the wetting behavior as a function of various parameters of the treatment was performed. The wettability of treated surfaces is strongly affected by surface roughness created after this treatment. The relationship between morphological parameters and wettability was discussed. Finally, the influence of sandblasting processing parameters on the mechanical behavior in monotoning and long‐term (fatigue tests) of the adhesive joint strength was studied, using single lap shear tests specimens. This has led to the proposal of specific surface morphological parameters for the optimization of the mechanical behavior of the adhesive joint of PEEK and its composites.
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Temps de cohérence temporelle de structures turbulentes porteuses de scalaires passifs au sein d'une turbulence homogène quasi-isotrope / Coherence times of passive scalar space scales in homogeneous and quasi-isotropic turbulenceLenoir, Jean-Michel 18 July 2011 (has links)
Le but principal du présent travail est ainsi de réaliser une expérience de mélange par la turbulence, dans laquelle il est possible de déterminer et de quantifier les temps de cohérence des différentes échelles spatiales des fluctuations du champ de vitesse et du champ de concentration qu'il transporte et mélange. La turbulence est ici voisine de la situation idéale statistiquement homogène et isotrope, et la configuration est conçue pour qu'il en soit de même pour le champ de concentration. La turbulence est créée par une grille placée perpendiculairement à un écoulement uniforme à l'extérieur des couches limites qui se développent le long des parois de la veine d'essais à section carrée constante. L'écoulement de la présente étude est un écoulement d'eau, dans lequel le champ de concentration est celui d'une solution de Rhodamine B injectée au niveau de la grille à travers des injecteurs équi-répartis le long des barreaux de celle-ci. Ce choix, dicté par la technique de mesure du champ de concentration par Fluorescence Induite par Laser, permet en outre de mesurer le champ de vitesse par une autre technique optique, elle aussi non-intrusive. Pour se rapprocher le plus de la théorie d'un mélange idéal statistiquement homogène et isotrope sans vitesse moyenne, on considère dans l'expérience, conformément à l'hypothèse de Taylor, que toutes les échelles associées à chacun de ces champs, sont convectés à la vitesse moyenne U de l'écoulement, et l'on suit une "boîte de turbulence" qui se déplace à cette vitesse le long de la veine. Par suite déterminer l'état de la turbulence en un point donné de cette boite à l'instant t et à l'instant t'=t+dt, revient à l'étudier dans l'expérience à t à l'abscisse x de la veine d'essai, et à t' à l'abscisse x+dx , avec dx=Udt, où se trouve le point de la boîte aux deux instants successifs. Les résultats expérimentaux concernant les échelles pour lesquelles l'isotropie statistique est satisfaite, permettent alors de vérifier une phénoménologie de l'évolution de la cohérence temporelle des diverses échelles spatiales du champ des fluctuations de concentration fondée sur les idées de Comte-Bellot et Corrsin. Cette expérience, est en outre l'occasion de donner des résultats sur les densités de probabilité de diverses propriétés statistiques des champs de fluctuation de vitesse. / The main purpose of this work is to make an experiment of mixing by turbulence, in which it is possible to determine and quantify the coherence time of the different spatial scales of fluctuations of a scalar field. We measure concentration fluctuations of rhodamine B by Planar Laser Induced Fluorescence (PLIF) which is transported and mixed by velocity fluctuations. These latter ones are generated by a grid placed perpendicularly to the flow in a water channel and are measured by Particle Image Velocimetry (PIV). The concentration field is injected in the flow by injectors regularly spaced on the grid so that it is a situation where both the velocity and the concentration fields are statistically homogeneous and isotropic. To get as close as the theory of statistically homogeneous and isotropic turbulence with no mean velocity, we consider, according to Taylor's hypothesis, that all scales associated with each of these fields are convected with the mean velocity U of the flow, and we follow a "turbulent box" that moves at U along the channel. As a result determining the state of turbulence at a given point of the box at time t and time t ' = t + dt, is like studying in the experiment at time t and space x of test section, and time t' and space x + dx of the test section, with dx = U dt. When statistical isotropy is satisfied, we can verify a phenomenology of the evolution of the temporal coherence of various space scales of the concentration fluctuation fields based on the ideas of Comte-Bellot and Corrsin. This experiment is also an opportunity to give results on probability densities of various statistical properties of fluctuating velocity fields.
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A New AC-Radio Frequency Heating Calorimetry Technique for Complex FluidsBarjami, Saimir 28 April 2005 (has links)
We have developed a new modulation calorimetry technique using RF-Field heating. This technique eliminates temperature gradients across the sample leading to a higher precision in evaluating the heat capacity compared to the previous techniques. A frequency scan was carried out on a 8CB+aerosil sample showing a wide plateau indicating the region of frequency independent heat capacity. A temperature scan was then performed through the first-order nematic to isotropic and second order smectic-A to nematic transitions and was shown to be consistent with the previous work. The amplitude of the RF heating power applied to the sample depends on the permittivity and the loss factor of the sample. Since the permittivity of a dielectric material has a strong temperature dependence in liquid crystals, new information is obtained. The heat capacity measurements have a relative resolution of better than 0.06%, and the phase shift a resolution of 0.03%, were shown to be significant improvements over traditional heating methods. We then applied this new RF calorimetry on bulk and aerosil 8CB dispersions. For the bulk 8CB, the step-like character of smectic-A to nematic transition, and first order nematic to isotropic transitions indicated the strong dominance of the permittivity and the loss factor of the material. For the 8CB+aerosil samples at different silica density, our data were consistent with the previous work and provides clear evidence for the coupling between the smectic-A and nematic phases. We have undertaken a combined T-dependent optical and calorimetric investigation of CCN47+aerosil samples through the I-N transition over a range of silica densities displaying the double I-N transition peak. This work offers compelling evidence that the I-N transition with weak quenched random disorder proceeds via a two-step process in which random-dilution is followed by random-field interactions on cooling from the isotropic phase, a previously unrecognized phenomena.
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Verformungsverfestigung bei zyklisch inkrementeller Torsion von Reineisen und dem Stahl 42CrMo4N / Strain hardening of pure iron and steel 42CrMo4N under cyclic incremental torsionKuprin, Corinna 12 February 2013 (has links) (PDF)
Die Arbeit widmet sich dem Fließverhalten von Stählen bei zyklisch inkrementeller Torsion. Dazu werden vergleichend Reineisen und der ferritisch-perlitische Stahl 42CrMo4N bei unterschiedlichen Verformungspfaden betrachtet. Vor allem in zyklischen Torsionsversuchen mit bleibendem Verformungsinkrement je Zyklus werden Fließkurvenverläufe und Verformungsverfestigung analysiert.
Die Ergebnisse belegen den Einfluss des lamellaren Zementit auf das Fließverhalten des Stahls 42CrMo4N, während die Eigenschaften des Reineisens von der entstehenden Versetzungszellstruktur bestimmt werden. Die Richtungsabhängigkeit der Fließspannung und die Verläufe der Fließkurven unterscheiden sich für die betrachteten Werkstoffe deutlich.
Fließortkurven dienen der quantitativen Beschreibung der Verfestigung. Die Vorgehensweise zu ihrer Ermittlung und ihre Abhängigkeit von den Versuchsbedingungen und den Verformungszuständen werden gezeigt. Bei Reineisen dominieren isotrope, bei dem Stahl 42CrMo4N kinematische Verfestigungsanteile das Fließverhalten. / Ferritic-pearlitic steel 42CrMo4N and pure iron under different strain paths are compared regarding their flow behaviour. Mainly in cyclic torsion tests with resulting strain increment per cycle shear stresses and strain hardening are analysed.
The results show, that the cementite lamellae determine the flow behaviour of the steel 42CrMo4N, whereas the properties of pure iron are governed by the evolving dislocation cell structure. The dependency of flow stress on the strain direction is different for the two materials.
Yield surfaces describe strain hardening quantitatively. The procedure for yield point detection and the dependency of subsequent yield surfaces on experimental conditions and strain states is shown. For pure iron isotropic hardening, for steel 42CrMo4N kinematic strain hardening dominates the flow behaviour.
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Slow Dynamics In Soft Condensed Matter : From Supercooled Liquids To Thermotropic Liquid CrystalsChakrabarti, Dwaipayan 06 1900 (has links)
This thesis, which contains fourteen chapters in two parts, presents theoretical and computer simulation studies of dynamics in supercooled liquids and thermotropic liquid crystals. These two apparently diverse physical systems are unified by a startling similarity in their complex slow dynamics. Part I consists of six chapters on supercooled liquids while Part II comprises seven chapters on thermotropic liquid crystals. The fourteenth chapter provides a concluding note.
Part I starts with an introduction to supercooled liquids given in chapter 1. This chapter discusses basic features of supercooled liquids and the glass transition and portrays some of the theoretical frameworks and formalisms that are widely recognized to have contributed to our present understanding.
Chapter 2 introduces a new model of binary mixture in order to study dynamics across the supercooled regime. The system consists of an equimolar mixture of the Lennard-Jones spheres and the Gay-Berne ellipsoids of revolution, and thus one of its components has orientational degrees of freedom (ODOF). A decoupling between trans-lational diffusion and rotational diffusion is found to occur below a temperature where the second rank orientational correlation time starts showing a steady deviation from the Arrhenius temperature behavior. At low temperatures, the optical Kerr effect (OKE) signal derived from the system shows a short-to-intermediate time power law decay with a very weak dependence on temperature, if at all, of the power law exponent as has been observed experimentally. At the lowest temperature investigated, jump motion is found to occur in both the translational and orientational degrees of freedom.
Chapter 3 studies how the binary mixture, introduced in the previous chapter, explores its underlying potential energy landscape. The study reveals correlations between the decoupling phenomena, observed almost universally in supercooled molecular liquids, and the manner of exploration of the energy landscape of the system. A significant deviation from the Debye model of rotational diffusion in the dynamics of ODOF is found to begin at a temperature at which the average inherent structure energy of the system starts falling as the temperature decreases. Further, the coupling between rotational diffusion and translational diffusion breaks down at a still lower temperature, where a change occurs in the temperature dependence of the average inherent structure energy.
Chapters 4-6 describe analytical and numerical approaches to solve kinetic models of glassy dynamics for various observables. The β process is modeled as a thermally activated event in a two-level system and the a process is described as a β relaxation mediated cooperative transition in a double-well. The model resembles a landscape picture, conceived by Stillinger [Science 267, 1935 (1995)], where the a process is assumed to involve a concerted series of the β processes, the latter being identified as elementary relaxations involving transitions between contiguous basins. For suitable choice of parameter values, the model could reproduce many of the experimentally observed features of anomalous heat capacity behavior during a temperature cycle through the glass transition as described in chapter 4. The overshoot of the heat capacity during the heating scan that marks the glass transition is found to be caused by a delayed energy relaxation. Chapter 5 shows that the model can also predict a frequency dependent heat capacity that reflects the two-step relaxation behavior. The high-frequency peak in the heat capacity spectra appears with considerably larger amplitude than the low-frequency peak, the latter being due to the a relaxation. The model, when simplified with a modified description of the a process that involves an irreversible escape from a metabasin, can be solved analytically for the relaxation time. This version of the model captures salient features of the structural relaxation in glassy systems as described in chapter 6.
In Part II, thermotropic liquid crystals are studied in molecular dynamics simulations using primarily the family of the Gay-Berne model systems. To start with, chapter 7 provides a brief introduction to thermotropic liquid crystals, especially from the perspective of the issues discussed in the following chapters. This chapter ends up with a detail description of the family of the Gay-Berne models.
Chapter 8 demonstrates that a model system for calamitic liquid crystal (comprising rod-like molecules) could capture the short-to-intermediate time power law decay in the OKE signal near the isotropic-nematic (I-N) phase transition as observed experimentally. The single-particle second rank orientational time correlation function (OTCF) for the model liquid crystalline system is also found to sustain a power law decay regime in the isotropic phase near the I-N transition. On transit across the I-N phase boundary, two power law decay regimes, separated by a plateau, emerge giving rise to a step-like feature in the single-particle second rank OTCF. When the time evolution of the rotational non-Gaussian parameter is monitored as a diagnostic of spatially heterogeneous dynamics, a dominant peak is found to appear following a shoulder at short times, signaling the growth of pseudonematic domains. These observations are compared with those relevant ones obtained for the supercooled binary mixture, as discussed in chapter 2, in the spirit of the analogy suggested recently by Fayer and coworkers [J. Chem. Phys. 118, 9303 (2003)].
In chapter 9, orientational dynamics across the I-N transition are investigated in a variety of model systems of thermotropic liquid crystals. A model discotic system that consists of disc-like molecules as well as a lattice system have been considered in the quest of a universal short-to-intermediate time power law decay in orientational relaxation, if any. A surprisingly general power law decay at short to intermediate times in orientational relaxation is observed in all these systems. While the power law decay of the OKE signal has been recently observed experimentally in calamitic systems near the I-N phase boundary and in the nematic phase by Fayer and coworkers [J. Chem. Phys. 116, 6339 (2002), J. Phys. Chem. B 109, 6514 (2005)], the prediction for the discotic system can be tested in experiments.
Chapter 10 presents the energy landscape view of phase transitions and slow dynamics in thermotropic liquid crystals by determining the inherent structures of a family of one-component Gay-Berne model systems. This study throws light on the interplay between the orientational order and the translational order in the mesophases the systems exhibit. The onset of the growth of the orientational order in the parent phase is found to induce a translational order, resulting in a smectic-like layer in the underlying inherent structures. The inherent structures, surprisingly, never seem to sustain orientational order alone if the parent nematic phase is sandwiched between the high-temperature isotropic phase and the low-temperature smectic phase. The Arrhenius temperature dependence of the orientational relaxation time breaks down near the I-N transition and this breakdown is found to occur at a temperature below which the system explores increasingly deeper potential energy minima. There exists a remarkable similarity in the manner of exploration of the potential energy landscape between the Gay-Berne systems studied here and the well known Kob-Andersen binary mixture reported previously [Nature, 393, 554 (1998)].
In search of a dynamical signature of the coupling between orientational order and translational order, anisotropic translational diffusion in the nematic phase has been investigated in the Gay-Berne model systems as described in chapter 11. The translational diffusion coefficient parallel to the director D// is found to first increase and then decrease as the temperature drops through the nematic phase. This reversal occurs where the smectic order parameter of the underlying inherent structures becomes significant for the first time. The non-monotonic temperature behavior of D// can thus be viewed from an energy landscape analysis as a dynamical signature of the coupling between orientational and translational order at the microscopic level. Such a view is likely to form the foundation of a theoretical framework to explain the anisotropic translation diffusion.
Chapter 12 investigates the validity of the Debye model of rotational diffusion near the I-N phase boundary with a molecular dynamics simulation study of a Gay-Berne model system for calamitic liquid crystals. The Debye model is found to break down near the I-N phase transition. The breakdown, unlike the one observed in supercooled molecular liquids where a jump diffusion model is often invoked, is attributed to the growth of orientational pair correlation. A mode-coupling theory analysis is provided in support of the explanation.
Chapter 13 presents a molecular dynamics study of a binary mixture of prolate ellipsoids of revolution with different aspect ratios interacting with each other through a generalized Gay-Berne potential. Such a study allows to investigate directly the aspect ratio dependence of the dynamical behavior.
In the concluding note, chapter 14 starts with a brief summary of the outcome of the thesis and ends up with suggestion of a few relevant problems that may prove worthwhile to be addressed in future.
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