The thesis involves computer simulation and theoretical studies of dynamics of water under confinement and structural transformation in different complex systems. Based on the systems and phenomena of interest, the work has been classified in to three major parts: I. Dynamics of water under confinement II. Dynamics of water in presence of amphiphilic solutes III. Structural transformation in complex systems The three parts have further been divided into nine chapters. Brief chapter wise outline of the thesis is discussed below. Part I deals with the dynamics of water in confined systems. In Chapter I.1, we provide a brief introduction of water dynamics inc on fined systems. We also give a brief outline of relevant experimental and theoretical techniques used to study the water dynamics under confinement. Chapter I.2 describes a model based analytical study of dynamical correlation in confined systems. Here, we introduce a novel one dimensional Ising model to investigate the propagation and annihilation of dynamical correlations in confined systems and to understand the intriguing shortening of the orientational relaxation time that has been reported for small sized reverse micelles (RMs).In our model, the two spins located at the two end cells are oriented in the opposite directions to mimic the surface effects present in the real systems. These produce opposing polarizations which propagate from the surface to the center, thus producing bulk like condition at the center. This model can be solved analytically for short chains. For long chains, we solve the model numerically with Glauber spin flip dynamics (and also with Metropolis single-spin flip Monte Carlo algorithm).We show that the model satisfactorily reproduces many of the features observed in experiments. Due to the destructive interference among correlations that propagate from the surface to the core, one of the rotational relaxation time components decays faster than the bulk. In general, the relaxation of spins is non-exponential due to the interplay between various interactions. In the limit of strong coupling between the spins or in the limit of low temperature, the nature of the relaxation of spins undergoes a change with the emergence of homogeneous dynamics, where the decay is predominantly exponential. In Chapter I.3, layer-wise distance dependent orientation relaxation of water confined in reverse micelle s(RM)is studied using theoretical and computational tools. We use both a newly constructed spins on a ring (SOR) Ising-type model with modified Shore-Zwanzig rotational dynamics and atomistic simulations with explicit water. Our study explores the size effect of RMs and the role of intermolecular correlations, compromised by the presence of a highly polar surface, on the distance (from the surface) dependence of water relaxation. The SOR model can capture some aspects of distance dependent orientation relaxation, such as acceleration of orientation relaxation at intermediate layers. In atomistic simulations, layer-wise decomposition of hydrogen bond (H-bond) formation pattern clearly reveal that the H-bond arrangement of water at a certain distance away from the surface can remain frustrated due to interaction with the polar surface head groups. We show that this layer-wise analysis also reveals the presence of a non-monotonic, slow relaxation component which can be attributed to the frustration effect and is accentuated in small to intermediate size RMs. For larger RMs, the long-time component decreases monotonically from the interface to the interior of the RMs with slowest relaxation observed at the interface. In ChapterI.4, we present theoretical two dimensional infrared spectroscopic (2D-IR) studies of water confined within RMs of various sizes. Here we focus again mainly on the altered dynamics of confined water by performing a layer-wise decomposition of water. We aim to quantify the relative contributions to the calculated 2D-IR spectra by water molecules located in different layers. The spectra of 0-1 transition clearly show substantial elongation along the diagonal, due to in homogeneous broadening and incomplete spectral diffusion, in the surface water layer of different size of RMs studied in this work. Our study reveals that the motion of the surface water molecules is sub-diffusive, establishing the constrained nature of their dynamics. This is further supported by the two peak nature of the angular analogue of the van Hove correlation function. With increasing system size the motion of water molecules becomes more diffusive in nature and the structural diffusion is observed to be almost completed in the central layer of larger RMs. Comparisons between experiment and simulation help establishing the correspondence between the spectral decomposition available in experimental 2D-IR with the spatial decomposition of simulated 2D-IR. Simulations also allow a quantitative exploration of the relative role of water, sodium ions and sulfonate head groups in irrational dephasing. Interestingly, the negative cross correlation between forces on oxygen and hydrogen of O-H bond in bulk water significantly decreases in the surface layer of different RMs. This negative cross correlation gradually increases in the central layer with increasing size of the RMs and this is found to be partly responsible for the faster relaxation rate of water in the central layer. Part II consists of two chapters and focuses on the dynamics of water in presence of amphiphilic solutes. In Chapter II.1, we present a brief introduction of water – DMSO binary mixture and various anomalous properties of the same. In Chapter II.2, we present theoretical IR study of water dynamics in water–DMSO binary mixtures of different compositions. We show that with increasing DMSO concentration, the IR absorption peak maxima show the presence of structural transformation in similar concentration range, observed in earlier studies. Analysis of H-bonded network near hydrophilic and hydrophobic part of DMSO also suggests that average number of hydrogen bonds near the hydrophobic parts possess maxima at the same concentration range. We also show that with increasing DMSO concentration water dynamics becomes very slow. This has been supported by the diagonal elongation of the 2D-IR spectra and also the slow decay of frequency fluctuation correlation n function (FFCF) and the orientation time correlation function (OTCF). The decoupling of the OTCF establishes that water-DMSOH-bond is much stronger than that of water-water. The last part (Part III) consists of three chapters that deal with structural transformation in various complex systems. In Chapter III.1, we introduce polydisperse systems and present existing theoretical, computer simulation and experimental studies. It also contains the importance and diversity of polydisperse system in nature. In Chapter III.2, we present computer simulation study of melting of polydisperse Lennard-Jones (LJ) system with Gaussian polydispersity in size. The phase diagram reproduces the existence of an early temperature in variant terminal polydispersity (δt0.11), with no signature of re-entrant melting. The absence of re-entrant melting can be attributed to the influence of attractive part of the potential on melting. We find that at terminal polydispersity the fractional density change approaches zero that seems to arise from vanishingly small compressibility of the disordered phase. At constant temperature and volume fraction system undergoes a sharp transition from crystalline solid to disordered state with increasing polydispersity. This has been quantified by second and third order rotational invariant bond orientational orders as well as by the average inherent structure energy. The translational order parameter also indicates similar structural change The free energy calculation further supports the nature of the transition. The third order bond orientational order shows that with increasing polydispersity, local cluster favors more icosahedral-like arrangements and thus the system loses its crystalline symmetry. In Chapter III.3, we present study of phase transition and effect of confinement on it in SOR model. This system is similar to our SOR model discussed in Chapter I.3. The spins execute continuous rotation under a modified XY Hamiltonian. In order to understand the nature of phase transition in such confined spin systems we have performed extensive Monte Carlo simulations. The system size dependence of Binders cumulant, specific heat, order parameter and finite size scaling of order parameter universally suggest the existence of a phase transition. The absence of hysteresis and Scaling of Binders energy cumulant minimum confirm the continuous nature of the transition. The finite size scaling analyses give rise to the mean field nature of the transition. Plausible applications of the proposed model in modeling dipolar liquids in confined systems are also discussed. In Appendix A, we discuss a preliminary study of front propagation in a non-equilibrium system. The model system analogous to the super cooled liquid shows non-Avrami domain growth during rejuvenation. The origin of the non-Avrami nature of the domain growth and the presence of cross over are also discussed. In Appendix B, we discuss umbrella a sampling technique and WHAM analysis which is used in ChapterIII.2 to get the free energy of polydisperse LJ system.

Les comportements critiques des systèmes de mécanique statistique en 2 dimensions ou de mécanique quantique en 1+1 dimensions, ainsi que certains aspects des systèmes sans interactions en 2+1 dimensions, sont efficacement décrits par les méthodes de la théorie des champs conforme et de l'intégrabilité, dont le développement a été spectaculaire au cours des 40 dernières années. Plusieurs problèmes résistent cependant toujours à une compréhension exacte, parmi lesquels celui de la transition entre plateaux dans l'Effet Hall Quantique Entier. La raison principale en est que de tels problèmes sont généralement associés à des théories non unitaires, ou théories conformes logarithmiques, dont la classification se révèle être d'une grande difficulté mathématique. Se tournant vers la recherche de modèles discrets (chaînes de spins, modèles sur réseau), dans l'espoir en particulier d'en trouver des représentations en termes de modèles exactement solubles (intégrables), on se heurte à la deuxième difficulté représentée par le fait que les théories associées sont la plupart du temps non compactes, ou en d'autres termes qu'elles donnent lieu à un continuum d'exposants critiques. En effet, le lien entre modèles discrets et théories des champs non compactes est à ce jour loin d'être compris, en particulier il a longtemps été cru que de telles théories ne pouvaient pas émerger comme limites continues de modèles discrets construits à partir d'un ensemble compact de degrés de libertés, par ailleurs les seuls qui donnent a accès à une construction systématique de solutions exactes.Dans cette thèse, on montre que le monde des modèles discrets compacts ayant une limite continue non compacte est en fait beaucoup plus grand que ce que les quelques exemples connus jusqu'ici auraient pu laisser suspecter. Plus précisément, on y présente une solution exacte par ansatz de Bethe d'une famille infinie de modèles(les modèles $a_n^{(2)}$, ainsi que quelques résultats sur les modèles $b_n^{(1)}$, où il est observé que tous ces modèles sont décrits dans un certain régime par des théories conformes non compactes. Parmi ces modèles, certains jouent un rôle important dans la description de phénomènes physiques, parmi lesquels la description de polymères en deux dimensions avec des interactions attractives et des modèles de boucles impliqués dans l'étude de modèles de Potts couplés ou dans une tentative de description de la transition entre plateaux dans l'Effet Hall par un modèle géométrique compact.On montre que l'existence insoupçonnéede limite continues non compacts pour de tels modèles peut avoir d'importantes conséquences pratiques, par exemple dans l'estimation numérique d'exposants critiques ou dans le résultats de simulations de Monte Carlo. Nos résultats sont appliqués à une meilleure compréhension de la transition theta décrivant l'effondrement des polymères en deux dimensions, et des perspectives pour une potentielle compréhension de la transition entre plateaux en termes de modèles sur réseaux sont présentées. / The critical points of statistical mechanical systems in 2 dimensions or quantum mechanical systems in 1+1 dimensions (this also includes non interacting systems in 2+1 dimensions) are effciently tackled by the exact methods of conformal fieldtheory (CFT) and integrability, which have witnessed a spectacular progress during the past 40 years. Several problems have however escaped an exact understanding so far, among which the plateau transition in the Integer Quantum Hall Effect,the main reason for this being that such problems are usually associated with non unitary, logarithmic conformal field theories, the tentative classification of which leading to formidable mathematical dificulties. Turning to a lattice approach, andin particular to the quest for integrable, exactly sovable representatives of these problems, one hits the second dificulty that the associated CFTs are usually of the non compact type, or in other terms that they involve a continuum of criticalexponents. The connection between non compact field theories and lattice models or spin chains is indeed not very clear, and in particular it has long been believed that the former could not arise as the continuum limit of discrete models built out of acompact set of degrees of freedom, which are the only ones allowing for a systematic construction of exact solutions.In this thesis, we show that the world of compact lattice models/spin chains with a non compact continuum limit is much bigger than what could be expected from the few particular examples known up to this date. More precisely we propose an exact Bethe ansatz solution of an infinite family of models (the so-called $a_n^{(2)}$ models, as well as some results on the $b_n^{(1)}$ models), and show that all of these models allow for a regime described by a non compact CFT. Such models include cases ofgreat physical relevance, among which a model for two-dimensional polymers with attractive interactions and loop models involved in the description of coupled Potts models or in a tentative description of the quantum Hall plateau transition by somecompact geometrical truncation. We show that the existence of an unsuspected non compact continuum limit for such models can have dramatic practical effects, for instance on the output of numerical determination of the critical exponents or ofMonte-Carlo simulations. We put our results to use for a better understanding of the controversial theta transition describing the collapse of polymers in two dimensions, and draw perspectives on a possible understanding of the quantum Hall plateautransition by the lattice approach.

La relativité générale représente la description la plus précise de l'interaction gravitationnelle. Cependant, alors que la matière est régie par les lois de la mécanique quantique, la gravitation, elle, est une théorie fondamentalement classique. A l'échelle de Planck, c'est-à-dire à des distances d'environ 10E-35 mètres, les effets quantiques et ceux de la gravitation deviennent tous deux importants. A l'heure actuelle, un langage mathématique unifié et décrivant les effets physiques à cette échelle est toujours manquant. Il existe néanmoins plusieurs théories candidates à cette description, et l'une d'entre elles, la gravité quantique à boucles, est l'objet d'étude de cette thèse.Afin de tester si une théorie candidate peur fournir une description appropriée des propriétés quantiques du champ de gravitation, elle doit présenter une certaine cohérence interne du point de vue mathématique, et aussi être en accord avec les tests expérimentaux de la relativité générale. Le but de cette thèse est de développer certains outils mathématiques qui éclairent ces conditions de consistance interne, et qui permettent d'établir un lien entre différentes formulations de la théorie. / General relativity is the most precise theory of the gravitational interaction. It is a classical field theory. All matter, on the other hand, follows the rules of quantum theory. At the Planck scale, at about distances of the order of 10E-35 meters, both theories become equally important. Today, theoretical physics lacks a unifying language to explore what happens at this scale, but there are several candidate theories available. Loop quantum gravity is one them, and it is the main topic of this thesis. To see whether a particular proposal is a viable candidate for a quantum theory of the gravitational field it must be free of internal inconsistencies, and agree with all experimental tests of general relativity. This thesis develops mathematical tools to check these.

In our pursuit of ever smaller transistors, with greater computational throughput, many questions arise about how material properties change with size, and how these properties may be modelled more accurately. Metallic nanocontacts, especially those for which magnetic properties are important, are of great interest due to their potential spintronic applications. Yet, serious challenges remain from the standpoint of theoretical and computational modelling, particularly with respect to the coupling of the spin and lattice degrees of freedom in ferromagnetic nanocontacts in emerging spintronic technologies. In this thesis, an extended method is developed, and applied for the first time, to model the interplay between magnetism and atomic structure in transition metal nanocontacts. The dynamic evolution of the model contacts emulates the experimental approaches used in scanning tunnelling microscopy and mechanically controllable break junctions, and is realised in this work by classical molecular dynamics and, for the first time, spin-lattice dynamics. The electronic structure of the model contacts is calculated via plane-wave and local-atomic orbital density functional theory, at the scalar- and vector-relativistic level of sophistication. The effects of scalar-relativistic and/or spin-orbit coupling on a number of emergent properties exhibited by transition metal nanocontacts, in experimental measurements of conductance, are elucidated by non-equilibrium Green’s Function quantum transport calculations. The impact of relativistic effects during contact formation in non-magnetic gold is quantified, and it is found that scalar-relativistic effects enhance the force of attraction between gold atoms much more than between between atoms which do not have significant relativistic effects, such as silver atoms. The role of non-collinear magnetism in the electronic transport of iron and nickel nanocontacts is clarified, and it is found that the most-likely conductance values reported for these metals, at first- and lastcontact, are determined by geometrical factors, such as the degree of covalent bonding in iron, and the preference of a certain crystallographic orientation in nickel. / Physics / Ph. D. (Physics)

Cette thèse exploite les liens profonds entre la physique des systèmes quantiques locaux, les propriétés non locales de leurs états fondamentaux et le contenu en information de ces états. Les deux premiers chapitres sont consacrés à l’application des systèmes quantiques locaux pour les fins d’une tâche informationnelle précise, soit le calcul quantique. Au terme d’un bref survol de la théorie, nous proposons un patron pour le calcul quantique universel et évolutif pouvant être réalisé sur une grande variété de plateformes physiques, et démontrons qu’il est particulièrement résilient face à un bruit anisotrope. Les quatre derniers chapitres sont pour leur part consacrés à l’approche informationnelle des systèmes quantiques à corps multiples. Nous décrivons les principales propriétés des corrélations et de l’intrication dans les états fondamentaux des systèmes de dimensions réduites les plus courants, en distinguant systèmes non critiques et systèmes critiques. Nous montrons que ces propriétés sont fortement modifiées par la présence de frustration géométrique dans les chaînes de spins. Enfin, nous réalisons une analyse exhaustive des corrélations et de l’intrication dans les états fondamentaux de deux théories quantiques de champs non triviales. / This thesis exploits the deep connections between the physics of local quantum systems, the nonlocal features in their ground states, and the information content of these states. The first two chapters are dedicated to the application of local quantum systems for the purpose of a definite information-theoretical task, namely quantum computation. After a brief survey of the theory, we propose a scheme for scalable universal quantum computation that, we argue, could be implemented on a wide variety of physical platforms, and show that it is particularly resilient to anisotropic noise. The last four chapters are dedicated to the information-theoretical approach of many-body quantum systems. We describe the main properties of correlations and entanglement in the ground states of the most common low-dimensional many-body systems, distinguishing between noncritical systems and critical ones. We show how these properties can be dramatically modified by the presence of geometric frustration in spin chains. Finally, we perform an intensive study of correlations and entanglement in the ground states of two nontrivial one-dimensional quantum field theories.

Les sections efficaces neutroniques des noyaux de courte durée de vie sont des données cruciales pour la physique fondamentale et appliquée dans des domaines tels que la physique des réacteurs ou l’astrophysique nucléaire. En général, l’extrême radioactivité de ces noyaux ne nous permet pas de procéder à des mesures induites par neutrons. Cependant, il existe une méthode de substitution (« surrogate » dans la littérature) qui permet de déterminer ces sections efficaces neutroniques par l’intermédiaire de réactions de transfert ou de réactions de diffusion inélastique. Son intérêt principal est de pouvoir utiliser des cibles moins radioactives et ainsi d’accéder à des sections efficaces neutroniques qui ne pourraient pas être mesurées directement. La méthode est basée sur l’hypothèse de formation d’un noyau composé et sur le fait que la désexcitation ne dépend essentiellement que de l’énergie d’excitation et du spin et parité de l'état composé peuplé. Toutefois, les distributions de moments angulaires et parités peuplés dans des réactions de transfert et celles induites par neutrons sont susceptibles d’être différentes. Ce travail fait l’état de l’art sur la méthode substitution et sa validité. En général, la méthode de substitution fonctionne très bien pour extraire des sections efficaces de fission. Par contre, la méthode de substitution dédiée à la capture radiative est mise à mal par la comparaison aux réactions induites par neutrons. Nous avons réalisé une expérience afin de déterminer les probabilités de désexcitation gamma du 176Lu et du 173Yb à partir des réactions de substitution 174Yb(3He,p)176Lu* et 174Yb(3He,alpha)173Yb*, respectivement, et nous les avons comparées avec les probabilités de capture radiative correspondantes aux réactions 175Lu(n,gamma) et 172Yb(n,gamma) qui sont bien connues. Cette expérience a permis de comprendre pourquoi, dans le cas de la désexcitation gamma, la méthode de substitution donne des écarts importants par rapport à la réaction neutronique correspondante. Ce travail dans la région de terres rares a permis d'évaluer dans quelle mesure la méthode de substitution peut s’appliquer pour extraire des probabilités de capture dans la région des actinides. Des expériences précédentes sur la fission ont aussi pu être réinterprétées. Ce travail apporte donc un éclairage nouveau sur la méthode de substitution. / Neutron-induced cross sections of short-lived nuclei are needed for fundamental and applied physics as nuclear energy or astrophysics. However, very often the high radioactivity of the samples makes the direct measurement of these cross sections extremely difficult. The surrogate reaction method is an indirect way of determining neutron-induced cross sections through transfer or inelastic scattering reactions. This method presents the advantage that in some cases the target material is stable or less radioactive than the material required for a neutron-induced measurement. The method is based on the hypothesis that the excited nucleus is a compound nucleus whose decay depends essentially on its excitation energy and on the spin and parity state of the populated compound state. Nevertheless, the spin and parity population differences between the compound-nuclei produced in the neutron and transfer-induced reactions may be different. This work reviews the surrogate method and its validity. Neutron-induced fission cross sections obtained with the surrogate method are in general good agreement. However, it is not yet clear to what extent the surrogate method can be applied to infer radiative capture cross sections. We performed an experiment to determine the gamma-decay probabilities for 176Lu and 173Yb by using the surrogate reactions 174Yb(3He,p)176Lu* and 174Yb(3He,alpha)173Yb*, respectively, and compare them with the well-known corresponding probabilities obtained in the 175Lu(n,gamma) and 172Yb(n,gamma) reactions. This experiment provides answers to understand why, in the case of gamma-decay, the surrogate method gives significant deviations compared to the corresponding neutron-induced reaction. In this work, we have also assessed whether the surrogate method can be applied to extract capture probabilities in the actinide region. Previous experiments on fission have also been reinterpreted. Thus, this work provides new insights into the surrogate method.