No description available.

No description available.

No description available.

Results are presented from a series of simulations undertaken to determine the effect of a novel form of molecular biaxiality upon the phase behaviour of the well established Gay-Berne (GB) liquid crystal model. Firstly, the simulation of a bulk system interacting via the Internally-Rotated Gay-Berne (IRGB) potential, which offers a single-site representation of a molecule rigidly constrained into a zig-zag conformation, is presented. The results of simulations performed for systems of IRGB particles with an aspect ratio of 3:1 confirm that the introduction of biaxiality into the model results in the destabilisation of the orientationally ordered phases. For particles with a sufficiently pronounced zig-zag conformation, this results in the complete destabilisation of the smectic A phase and the smectic B phase being replaced by the tilted smectic J phase. Following these observations, the effect upon the phase behaviour of increasing molecular elongation is also considered, with an increase in the aspect ratio from 3:1 to 4:1 resulting in the nematic and smectic J phases being replaced by smectic A and smectic G phases respectively. Secondly, a version of the IRGB potential modified to include a degree of molecular flexibility is considered. Results obtained from bulk systems interacting via the flexible IRGB for 3:1 and 4:1 molecules show that the introduction of flexibility results in the destabilisation of the smectic A phase and the stabilisation of the nematic and tilted hexatic phases. Finally, the effect upon the phase behaviour of the rigid IRGB model of the inclusion of a longitudinal linear quadrupole is examined. These results show that increasing quadrupole moment results in the destabilisation of the tilted hexatic phase, although the biaxial order parameter is increased with increasing quadrupole moment. There is no clear correlation between quadrupole magnitude and the other observed phase transitions, with the nematic and smectic A phases being variously stabilised and destabilised with increasing quadrupole magnitude. For the 4:1 molecules with large quadrupole moments, buckled smectic layers are observed where some molecules are tilted with respect to a local layer normal. Of all the systems considered here, this buckled structure is the one which most closely resembles the elusive smectic C phase.

No / We address the problem of recognition and growth of ice nuclei in simulation of supercooled bulk water. Bond orientation order parameters based on the spherical harmonics analysis are shown to be ineffective when applied to ice nucleation. Here we present an alternative method which robustly differentiates between hexagonal and cubic ice forms. The method is based on accumulation of the maximum projection of bond orientations onto a set of predetermined vectors, where different terms can contribute with opposite signs with the result that the irrelevant or incompatible molecular arrangements are damped out. We also introduce an effective cluster size by assigning a quality weight to each molecule in an ice-like cluster. We employ our cluster analysis in Monte Carlo simulation of homogeneous ice formation. Replica-exchange umbrella sampling is used for biasing the growth of the largest cluster and calculating the associated free energy barrier. Our results suggest that the ice formation can be seen as a two-stage process. Initially, short tetrahedrally arranged threads and rings are present; these become correlated and form a diffuse ice-genic network. Later, hydrogen bond arrangements within the amorphous ice-like structure gradually settle down and simultaneously `tune-up¿ nearby water molecules. As a result, a well-shaped ice core emerges and spreads throughout the system. The process is very slow and diverse owing to the rough energetic landscape and sluggish molecular motion in supercooled water, while large configurational fluctuations are needed for crystallization to occur. In the small systems studied so far the highly cooperative molecular rearrangements eventually lead to a relatively fast percolation of the forming ice structure through the periodic boundaries, which inevitably affects the simulation results. / EPSRC

For centuries, scientists have dreamed of creating materials by design. Rather than discovery by accident, bespoke materials could be tailored to fulfill specific technological needs. Quantum theory and computational methods are essentially equal to the task, and computational power is the new bottleneck. Machine learning has the potential to solve that problem by approximating material behavior at multiple length scales. A full end-to-end solution must allow us to approximate the quantum mechanics, microstructure and engineering tasks well enough to be predictive in the real world. In this dissertation, I present algorithms and methodology to address some of these problems at various length scales. In the realm of enumeration, systems with many degrees of freedom such as high-entropy alloys may contain prohibitively many unique possibilities so that enumerating all of them would exhaust available compute memory. One possible way to address this problem is to know in advance how many possibilities there are so that the user can reduce their search space by restricting the occupation of certain lattice sites. Although tools to calculate this number were available, none performed well for very large systems and none could easily be integrated into low-level languages for use in existing scientific codes. I present an algorithm to solve these problems. Testing the robustness of machine-learned models is an essential component in any materials discovery or optimization application. While it is customary to perform a small number of system-specific tests to validate an approach, this may be insufficient in many cases. In particular, for Cluster Expansion models, the expansion may not converge quickly enough to be useful and reliable. Although the method has been used for decades, a rigorous investigation across many systems to determine when CE "breaks" was still lacking. This dissertation includes this investigation along with heuristics that use only a small training database to predict whether a model is worth pursuing in detail. To be useful, computational materials discovery must lead to experimental validation. However, experiments are difficult due to sample purity, environmental effects and a host of other considerations. In many cases, it is difficult to connect theory to experiment because computation is deterministic. By combining advanced group theory with machine learning, we created a new tool that bridges the gap between experiment and theory so that experimental and computed phase diagrams can be harmonized. Grain boundaries in real materials control many important material properties such as corrosion, thermal conductivity, and creep. Because of their high dimensionality, learning the underlying physics to optimizing grain boundaries is extremely complex. By leveraging a mathematically rigorous representation for local atomic environments, machine learning becomes a powerful tool to approximate properties for grain boundaries. But it also goes beyond predicting properties by highlighting those atomic environments that are most important for influencing the boundary properties. This provides an immense dimensionality reduction that empowers grain boundary scientists to know where to look for deeper physical insights.

No description available.

Chromonic liquid crystals are a relatively new class of lyotropic liquid crystals. In an effort to understand this lyotropic phase better, studies on the phase behavior, defects formed in these systems and characterization of the order were performed. We studied three chromonic liquid crystal materials in nematic and biphasic regions: Sunset Yellow FCF (SSY, a food dye), a cationic perylene diimide derivative (PDI, a conducting dye) and cromolyn sodium (DSCG, a drug). For SSY chromonics in the nematic region, order parameters ( and ) were obtained by polarized Raman measurements. Using the order parameters the flow behavior was predicted and was found to be non-flow aligning. A comprehensive viscoelastic property set of SSY chromonics was obtained by studying the statics and dynamics of defects during the formation of planar aligned monodomain. Applications of PDI thin films as vapor sensors were explored; anisotropic electronic properties of oriented PDI films show good conductivity along the columns presumably arising from the overlap between the ? systems. In the biphasic region, growth and fluctuation of SSY tactoids and interesting patterns of biphasic DSCG under capillary geometry were observed; elastic properties and surface tension were estimated based on the shape of DSCG tactoids. Polymer dispersed lyotropic chromonic liquid crystals with different drop shapes and director configurations were also fabricated using various water-soluble polymers.

Das Verstaendnis dafuer, welche Freiheitsgrade fuer das Eingeschlossensein der Quarks von Bedeutung sind, ist ein altbekanntes Problem. Da weithin angenommen wird, dass das Zentrum der Eichgruppe eine bedeutende Rolle spielt, ist es interessant, eine Theorie mit einem trivialen Zentrum zu untersuchen. Das einfachste Modell, um dieses Problem zu untersuchen, ist eine Theorie mit ungeradzahliger Dimension der Darstellung der Eichgruppe SU(2). Theorien mit einem trivialen Zentrum werden schon seit langer Zeit in zwei verschiedenen Diskretisierungen untersucht: die adjungierte Wilson-Wirkung und die Villain-Wirkung. Es stellte sich heraus, dass sie aus zweierlei Gruenden problematisch sind. Zunaechst zeigte sich, dass in beiden Fällen ein bulk-Phasenuebergang den physikalischen Phasenuebergang bei endlicher Temperatur ueberschattet. Darueberhinaus erwies es sich im Falle der Villain-Theorie, dass die Anwesenheit von Twist-Sektoren fuer die Konstruktion eines ergodischen Algorithmus problematisch sein kann. Die Gitter-Artefakte, die den bulk-Phasenuebergang verursachen, wurden mit Z(2) Monopolen identifiziert. Diese Monopole koennen mit Hilfe eines entsprechenden chemischen Potentials unterdrueckt werden. Eine erste Untersuchung des Phasenuebergangs bei endlicher Temperatur durch andere Autoren wurde nur im Falle der Villain-Wirkung durchgefuehrt, wobei in dieser Untersuchung die Twist-Sektoren ohne Beruecksichtigung blieben. In der vorliegenden Arbeit untersuchen wir nichtstoerungstheoretisch die Wilson-Wirkung in der adjungierten Darstellung der Eichgruppe SU(2) mit einem chemischen Potential, welches die Z(2)-Monopole bei nicht verschwindender Temperatur und bei Temperatur Null unterdrueckt. Wir untersuchen hierbei die Auswirkungen des chemischen Potentials lambda auf einige Observable. Fuer hinreichend grosse lambda zeigen die Observablen keine Diskontinuitaet in der adjungierten Kopplung. In diesem Gebiet des Phasendiagramms untersuchen wir, meist eingeschraenkt auf den trivialen Twist-Sektor, die Existenz eines Phasenuebergangs bei endlicher Temperatur. Um diesen Phasenuebergang zu identifizieren, gelingt es uns, einen neuen Ordungsparameter zu definieren, den wir erfolgreich auch in der fundamentalen Darstellung der SU(2) testen. Ferner analysieren wir die raeumliche Verteilung der fundamentalen Polyakov-loop-Variable und des Pisaer Unordnungs-Operators, welcher die Kondensation magnetischer Ladungen beschreibt. Die Ergebnisse, die wir mit diesen Untersuchungsmethoden erhielten, lassen auf einen vom bulk-Phasenuebergang entkoppelten Phasenuebergang bei endlicher Temperatur oder einen cross-over schliessen. / The understanding of which degrees of freedom are relevant for the confinement of quarks is a long standing problem. Since it is widely believed that the center of the gauge group plays an important role, it is interesting to study a theory with a trivial center. The simplest model to investigate this problem is provided by a theory in an odd-dimensional representation of the gauge group SU(2). Center-blind theories were studied long time ago in two different discretizations, the adjoint Wilson and the Villain action, and they turned out to be problematic for two reasons. In both cases a bulk phase transition was shown to overshadow the physical finite temperature one. Another feature, pointed out in the Villain case, was the presence of twist sectors, which could cause difficulties in the construction of an ergodic algorithm. The lattice artifacts responsible for the bulk phase transition were identified with Z(2) monopoles and they could be suppressed by the use of an appropriate chemical potential. A preliminary investigation of the finite temperature phase transition by other authors was done only in the Villain case and without taking care of the twist sectors. In this thesis we perform a lattice study of the Wilson action in the adjoint representation of the gauge group SU(2) with a chemical potential, which suppresses the Z(2) monopoles at zero and non-zero temperature. We investigate the effects of the chemical potential lambda on some observables. For large enough lambda at vanishing temperature the observables do not show any discontinuity in the adjoint coupling. In this region we study the existence of a finite temperature phase transition restricting ourselves mainly to the trivial twist sector. In order to detect this phase transition we are able to define a new order parameter, which we successfully test also for the case of the fundamental representation of SU(2). Furthermore we analyze the spatial distribution of the fundamental Polyakov loop and the Pisa disorder operator which detects the condensation of magnetic charges. These different tools provide an indication for a finite temperature phase transition or crossover decoupled from the bulk phase transition.

La spectroscopie RMN 2D du deutérium en abondance naturelle (DAN) en utilisant les cristaux liquides chiraux comme solvant de RMN est une méthodologie efficace pour deux raisons: i) l’interaction quadrupolaire (interaction RMN sensible à l’ordre orientationnel des molécules et spécifique aux noyaux de spin I>1/2) n’est plus nulle en moyenne comme dans les liquides; ii) la chiralité du milieu permet de discriminer spectralement des énantiomères (molécule chirale) ou des directions énantiotopes (molécule prochirale). L'objectif principal de ce travail de Thèse était d'explorer le potentiel analytique de cette technique pour analyser le fractionnement isotopique naturel deutérium dans le cas d’ester d’acides gras saturés (AGS) et (poly)insaturés (AGI). Le but ultime de ce travail est de fournir de nouvelles informations (de nature stéréochimique) pour améliorer la compréhension de certains mécanismes enzymatiques impliqués au cours de leur biosynthèse. Dans ce contexte, nous avons montré que l'utilisation de solutions organiques orientées de polypeptides (mésophases chirales) utilisant des co-solvants polaires comme le DMF ou la pyridine (Py) fournissait les meilleurs résultats en termes d’(énantio)discrimination spectrale (nombre de sites et amplitude) sur la base des déplacements chimiques et des éclatements quadrupolaires du deutérium. Ainsi, la mésophase chirale (PBLG/Py) a été utilisée avec succès pour analyser les AGI comme le linoléate de méthyle (C18), pour lequel nous avons pu mesurer l'excès énantio-isotopomèrique (eei) au niveau de chaque site méthylène de la molécule. Pour la première fois, d'importantes informations relatives à la stéréochimie des mécanismes enzymatiques, inaccessibles par la méthode conventionnelle SNIF-NMR®, ont été déterminées. La même méthodologie impliquant la mésophase achirale (PBG/Py) et chirale (PBLG/Py) s’est révélée également être un excellent outil pour l'analyse des SAFA sous leur forme libre (C14 à C18) ou sous leur forme de triglycérides (3*C4 et 3*C14). L'attribution des doublets 2H détectés sur les spectres RMN 2D anisotropes des SAFA a été confirmée par l'élaboration d'un modèle théorique capable de prédire le comportement orientationnel de ces molécules flexibles. Comme exemple illustratif, la méthode a été appliquée pour étudier les mécanismes enzymatiques convertissant le linoléate en vernoléate dans deux plantes différentes. Enfin, pour améliorer la compréhension des interactions «soluté-polypeptide» impliquées dans les mécanismes d'orientation et d’énantio-discrimination, nous avons étudié par RMN 2D DAN, l'évolution des paramètres d'ordre (matrice de Saupe) de deux molécules prochirales, rigides et apolaires dissoutes dans une mésophase chirale préparée en mélangeant deux polypeptides de même stéréochimie (L), mais dont la nature chimique des chaînes latérales est différente, en fonction de leur proportion massique respective. / Natural abundance deuterium (NAD) 2D-NMR spectroscopy using (a)chiral liquid crystals as NMR solvent is a powerful method for two reasons: i) the quadrupolar interaction (an order-sensitive NMR interaction specific to spins I > ½) is not averaged to zero anymore as in liquids; ii) the chirality of medium allows enantiomers (chiral molecule) or enantiotopic directions (prochiral molecule) to be spectrally discriminated. The main objective of this Thesis work was to explore the analytical potential of this technique to analyze the natural distribution of deuterium in the case of esters of saturated fatty acids (SAFA) and (poly)unsaturated fatty acids (PUFA). The ultimate goal of this research is to collect new (stereochemical) information to improve the understanding of some enzymatic mechanisms involved during their biosynthesis. In this context, we have shown that the use of oriented solutions of polypeptide (chiral mesophases) using polar co-solvents such as DMF or pyridine (py) provided better results in terms of spectral (enantio)discrimination (number of sites and magnitude) on the the basis of chemical shifts and deuterium quadrupole splittings. Thus, the chiral mesophase (PBLG/py) has been applied successfully to analyse PUFA’s like the methyl linoleate (C18) for which we could measure the enantio-isotopomeric excess (eie) at each methylen site of the molecule. For the first time, important information related to the stereochemistry of enzymatic mechanisms, inaccessible by the conventional method SNIF-NMR®, have been determined. The same methodology using achiral (PBG / py) and chiral (PBG / py) mesophases, revealed also to be an excellent tool for analysing SAFA in their free form (C14 to C18), or in triglyceride forms (3*C4 and 3*C14). The assignment of 2H doublets detected on 2D-NMR spectra of SAFA’s was confirmed by developing a theoretical model predicting the orientational ordering behavior of these flexible molecules. As illustrative exemple, the method was applied for investigating the enzymatic mechanisms converting the linoleate into vernoleate in two different plants. Finally, to improve the understanding of “solute/polypeptide" interactions involved in the orientation and enantiodiscrimination mechanisms, we have investigated by NAD 2D-NMR the evolution of the order parameters (Saupe matrix) of two apolar, rigid prochiral molecules dissolved in a chiral mesophase made by mixing two polypeptides having the same stereochemistry (L) but different type of side chains, versus their respective mass proportion.