Academic literature on the topic 'Isotropic phase of liquid crystals'

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.

Dissertation (Ph.D.) -- Worcester Polytechnic Institute.<br>Keywords: smectic-A to smectic-C; nematic to smectic-A; isotropic-nematic; phase transition; quenched random disorder; liquid crystal; gel structure; turbidity; gel dynamics; x-ray intensity fluctuation spectroscopy ( XIFS ); ac-calorimetry; x-ray diffraction Includes bibliographical references (p. 210-218).

Les liquides diffèrent des solides par une réponse retardée à la sollicitation en cisaillement; c’est-à-dire une absence d’élasticité de cisaillement et un comportement d'écoulement à basses fréquences (&lt;1 Hz). Ce postulat pourrait ne pas être vrai à toutes échelles. A l’échelle submillimétrique, les mesures viscoélastiques (VE) réalisées en améliorant l'interaction entre le liquide et le substrat, montrent qu’une élasticité basses-fréquences existe dans des liquides aussi variés que les polymères, les surfondus, les liquides à liaison H, ioniques ou van der Waals. Ce résultat implique que les molécules à l'état liquide ne seraient pas dynamiquement libres, mais élastiquement corrélées.En utilisant les propriétés biréfringentes des fluctuations prétransitionnelles qui coexistent dans la phase isotrope des cristaux liquides, nous montrons qu'il est possible de visualiser ces corrélations « cachées ». Dans des conditionssimilaires aux mesures VE, une biréfringence optique synchrone à la déformation est observée dans la phase isotrope à des fréquences aussi basses que 0.01 Hz et des températures éloignées de toute transition. Le comportement dela biréfringence basses-fréquences a des similitudes avec l'élasticité; elle est en phase avec la déformation à faibles amplitudes de déformation, puis en phase avec le taux de déformation à plus grandes amplitudes. La biréfringence basses- fréquences est forte, sans défaut et réversible. Elle indique un ordre à longue portée. La synchronisation de la réponse à la sollicitation en fréquence et l’état ordonné qu’elle produit ne sont pas compatibles avec un état liquide isotrope mais montrent qu’il s’agit d’un état élastique soumis à déformation (entropie élastique)<br>Liquids differ from solids by a delayed response to a shear mechanical solicitation; i.e. they have no shearelasticity and exhibit a flow behaviour at low frequency (&lt;1 Hz). This postulate might be not verified at thesub-millimeter scale. By optimizing the measurement in particular by improving the liquid/substrate interactions (wetting), a low frequency shear elasticity has been found in liquids including molten polymers, glass-formers, H-bond polar, ionic or van der Waals liquids. This result implies that molecules in the liquid state may not be dynamically free but weaklyelastically correlated. Using the birefringent properties of the pretransitional fluctuations coexisting in the isotropic phase of liquid crystals, we show that it is possible to visualize these “hidden” shear-elastic correlations. We detect a synchronized birefringent optical response in the isotropic phase that is observable at frequencies as low as 0.01 Hz and at temperatures far away from anyphase transition. The low-frequency birefringence exhibits a strain dependence similar to the low frequency elasticity: An optical signal that is in-phase with the strain at low strain amplitudes and in-phase with the strain-rate at larger strain amplitudes. The birefringent response is strong, defect-free, reversible and points out a collective response. This long-range ordering rules out the condition of an isotropic liquid and its synchronized response supports the existenceof long-range elastic (solid-like) correlations. In the light of this, the strain dependence of the harmonic birefringent signal and the shear elasticity may correspond to an entropy-driven transition

Com uma mistura de laurato de potássio, decanol e agua, determina-se a birrefringência induzida, na fase isotrópica, por gradientes de velocidade, no interior da amostra. Os movimentos são provocados através de vibrações periódicas nas paredes do porta amostras. O tempo de relaxação, da estrutura de rolos, e determinado experimental e teoricamente. É determinado, também, o parâmetro T AST (temperatura em torno da temperatura de transição), ate então desconhecido, em cristais líquidos liotrópicos. Como uma provável aplicação pratica, e proposta a confecção de dispositivos sensíveis a vibrações.<br>With a mixture of the Potassium Laurate, Decanol and water, the birefringence induced by gradient of the velocity, in the isotropic phase, is determinated. The movement are provocated through periodic vibrations of the superface of the sample holder. The relaxation time of the roll structure is determinated experimental an theorically. The temperature T* (temperature around the transition temperature), well-known in thermotropic liquid crystals, is determinated in liotropic liquid crystals. The confection of the sensible vibration dispositive is proposed.