Nanocrystalline (NC) metals and alloys are known to possess superior mechanical properties, e.g., strength, hardness, and wear-resistance, as compared to conventional microcrystalline materials. NC metals are characterized by a mean grain size <100 nm; in this grain size regime, inelastic deformation can occur via a combination of interface-mediated mechanisms viz., grain boundary sliding/migration, and dislocation nucleation from grain boundary sources. Recent studies have suggested that these interface-mediated inelastic deformation mechanisms in fcc metals are influenced by non-glide stresses and interfacial free volume, unlike dislocation glide mechanisms that operate in microcrystalline fcc metals. Further, observations of tension-compression strength asymmetry in NC metals raise the possibility that yield and inelastic flow in these materials may not be adequately described by solely the deviatoric stress. Unfortunately, most literature concerning the mechanical testing of NC metals is limited to uniaxial deformation or nanoindentation techniques, and the multiaxial deformation behavior is often predicted assuming initially isotropic yield and subsequent flow normal to the yield surface. The primary objective of this thesis is to obtain a better understanding of the nature of inelasticity in NC metals by simulating multiaxial deformation at the atomistic resolution, and developing methods to interpret the results in ways that would be useful from a continuum constitutive modeling viewpoint. First, we have presented a novel, statistical mechanics-based approach to unambiguously resolve the elastic-plastic transition as an avalanche in the proliferation of mobile defects. This approach is applied to nanocrystalline Cu to explore the influence of pressure and multiaxial stress states on the inelastic deformation behavior. The results suggest that initial yield in nanocrystalline Cu under biaxial loading is only weakly anisotropic in the 5 nm grain size regime, and that plastic flow evolves in a direction normal to the von Mises yield surface. However, triaxial deformation simulations reveal a significant effect of the superimposed hydrostatic stress on yielding under shear. These results are analyzed in detail in order to assess the influence of pre-existing internal stresses and interfacial excess volume on the inelastic deformation behavior. Further, we have studied the effects of imposed hydrostatic pressure on the shear deformation behavior of Cu bicrystals containing symmetric tilt interfaces, as well as Cu nanocrystals of different grain sizes. Most interfaces exhibit an increase in shear strength with imposed compressive hydrostatic pressure. However, for some interfaces, this trend is reversed. Neither the sign nor the magnitude of the pressure-induced elevation in shear strength appears to correlate with interface structure or particular deformation mechanism(s). In Cu nanocrystals, we observe that imposed compressive pressure leads to strengthening under shear deformation, and the effect of imposed pressure on the shear strength becomes stronger with increase in grain size or temperature. Activation parameters for shear deformation have been computed for these nanocrystals, and computed values seem to agree with existing experimental and theoretical estimates. Finally, we have proposed some modifications to conventional isothermal molecular dynamics algorithms, in order to isolate dislocation nucleation events from interfacial sources, and thereby permit explicit computation of the activation parameters for such events.

The topic of this thesis is a mathematically rigorous derivation of formulae for the magnetic force which is exerted on a part of a bounded magnetized body by its surrounding. Firstly, the magnetic force is considered within a continuous system based on macroscopic magnetostatics. The force formula in this setting is called Brown's force formula referring to W. F. Brown, who gave a mainly physically motivated discussion of it. This formula contains a surface integral which shows a nonlinear dependence on the normal. Brown assumes the existence of an additional term in the surface force which cancels the nonlinearity to allow an application of Cauchy's theorem in continuum mechanics to a magnetoelastic material. The proof of Brown's formula which is given in this work involves a suitable regularization of a hypersingular kernel and uses singular integral methods. Secondly, we consider a discrete, periodic setting of magnetic dipoles and formulate the force between a part of a bounded set and its surrounding. In order to pass to the continuum limit we start from the usual force formula for interacting magnetic dipoles. It turns out that the limit of the discrete force is different from Brown's force formula. One obtains an additional nonlinear surface term which allows one to regard Brown's assumption on the surface force as a consequence of the atomistic approach. Due to short range effects one obtains moreover an additional linear surface term in the continuum limit of the discrete force. This term contains a certain lattice sum which depends on a hypersingular kernel and the underlying lattice structure. / Das Thema dieser Arbeit ist eine mathematisch strenge Herleitung von Formeln für die magnetische Kraft, die auf einen Teil eines beschränkten, magnetischen Körpers durch seine Umgebung ausgeübt wird. Zunächst wird die magnetische Kraft in einem kontinuierlichen System auf Grundlage der makroskopischen Magnetostatik betrachtet. Mit Bezug auf W. F. Brown, der eine vor allem physikalisch motivierte Herleitung der Kraftformel gegeben hat, wird diese auch Brownsche Kraftformel genannt. Das Oberflächenintegral in dieser Formel zeigt eine nichtlineare Abhängigkeit von der Normalen. Um Cauchys Theorem aus der Kontinuumsmechanik in einem magnetoelastischen Material anwenden zu können, nimmt Brown an, dass die Oberflächenkraft einen zusäatzlichen Term enthält, der den nichtlinearen Ausdruck aufhebt. Der Beweis der Brownschen Kraftformel in dieser Arbeit beruht auf einer geeigneten Regularisierung eines hypersingulären Kerns und benutzt Methoden für singuläre Integrale. Danach gehen wir von einem diskreten, periodischen System von magnetischen Dipolen aus und betrachten die Kraft zwischen einem Teil einer beschränkten Menge und der Umgebung. Um zum Kontinuumslimes überzugehen, starten wir von der üblichen Kraftformel für wechselwirkende magnetische Dipole. Es zeigt sich, dass sich der Limes der diskreten Kraft von der Brownschen Kraftformel unterscheidet. Man erhält einen zusätzlichen nichtlinearen Oberflächenterm, der es ermöglicht, Browns Annahme als Konsequenz des atomistischen Zugangs zu sehen. Kurzreichweitige Effekte führen zudem zu einem linearen Oberflächenterm im Kontinuumlimes der diskreten Kraft. Dieser Zusatzterm enthält eine gewisse Gittersumme, die von einem hypersingulären Kern und der Struktur des zugrundeliegenden Gitters abhängt.

abstract: A hybrid molecular dynamics (MD) simulation framework is developed to emulate mechanochemical reaction of mechanophores in epoxy-based nanocomposites. Two different force fields, a classical force field and a bond order based force field are hybridized to mimic the experimental processes from specimen preparation to mechanical loading test. Ultra-violet photodimerization for mechanophore synthesis and epoxy curing for thermoset polymer generation are successfully simulated by developing a numerical covalent bond generation method using the classical force field within the framework. Mechanical loading tests to activate mechanophores are also virtually conducted by deforming the volume of a simulation unit cell. The unit cell deformation leads to covalent bond elongation and subsequent bond breakage, which is captured using the bond order based force field. The outcome of the virtual loading test is used for local work analysis, which enables a quantitative study of mechanophore activation. Through the local work analysis, the onset and evolution of mechanophore activation indicating damage initiation and propagation are estimated; ultimately, the mechanophore sensitivity to external stress is evaluated. The virtual loading tests also provide accurate estimations of mechanical properties such as elastic, shear, bulk modulus, yield strain/strength, and Poisson’s ratio of the system. Experimental studies are performed in conjunction with the simulation work to validate the hybrid MD simulation framework. Less than 2% error in estimations of glass transition temperature (Tg) is observed with experimentally measured Tgs by use of differential scanning calorimetry. Virtual loading tests successfully reproduce the stress-strain curve capturing the effect of mechanophore inclusion on mechanical properties of epoxy polymer; comparable changes in Young’s modulus and yield strength are observed in experiments and simulations. Early damage signal detection, which is identified in experiments by observing increased intensity before the yield strain, is captured in simulations by showing that the critical strain representing the onset of the mechanophore activation occurs before the estimated yield strain. It is anticipated that the experimentally validated hybrid MD framework presented in this dissertation will provide a low-cost alternative to additional experiments that are required for optimizing material design parameters to improve damage sensing capability and mechanical properties. In addition to the study of mechanochemical reaction analysis, an atomistic model of interphase in carbon fiber reinforced composites is developed. Physical entanglement between semi-crystalline carbon fiber surface and polymer matrix is captured by introducing voids in multiple graphene layers, which allow polymer matrix to intertwine with graphene layers. The hybrid MD framework is used with some modifications to estimate interphase properties that include the effect of the physical entanglement. The results are compared with existing carbon fiber surface models that assume that carbon fiber has a crystalline structure and hence are unable to capture the physical entanglement. Results indicate that the current model shows larger stress gradients across the material interphase. These large stress gradients increase the viscoplasticity and damage effects at the interphase. The results are important for improved prediction of the nonlinear response and damage evolution in composite materials. / Dissertation/Thesis / Doctoral Dissertation Mechanical Engineering 2017

This thesis addresses the sampling problem in a high-dimensional space, i.e., the computation of averages with respect to a defined probability density that is a function of many variables. Such sampling problems arise in many application areas, including molecular dynamics, multiscale models, and Bayesian sampling techniques used in emerging machine learning applications. Of particular interest are thermostat techniques, in the setting of a stochastic-dynamical system, that preserve the canonical Gibbs ensemble defined by an exponentiated energy function. In this thesis we explore theory, algorithms, and numerous applications in this setting. We begin by comparing numerical methods for particle-based models. The class of methods considered includes dissipative particle dynamics (DPD) as well as a newly proposed stochastic pairwise Nosé-Hoover-Langevin (PNHL) method. Splitting methods are developed and studied in terms of their thermodynamic accuracy, two-point correlation functions, and convergence. When computational efficiency is measured by the ratio of thermodynamic accuracy to CPU time, we report significant advantages in simulation for the PNHL method compared to popular alternative schemes in the low-friction regime, without degradation of convergence rate. We propose a pairwise adaptive Langevin (PAdL) thermostat that fully captures the dynamics of DPD and thus can be directly applied in the setting of momentum-conserving simulation. These methods are potentially valuable for nonequilibrium simulation of physical systems. We again report substantial improvements in both equilibrium and nonequilibrium simulations compared to popular schemes in the literature. We also discuss the proper treatment of the Lees-Edwards boundary conditions, an essential part of modelling shear flow. We also study numerical methods for sampling probability measures in high dimension where the underlying model is only approximately identified with a gradient system. These methods are important in multiscale modelling and in the design of new machine learning algorithms for inference and parameterization for large datasets, challenges which are increasingly important in "big data" applications. In addition to providing a more comprehensive discussion of the foundations of these methods, we propose a new numerical method for the adaptive Langevin/stochastic gradient Nosé-Hoover thermostat that achieves a dramatic improvement in numerical efficiency over the most popular stochastic gradient methods reported in the literature. We demonstrate that the newly established method inherits a superconvergence property (fourth order convergence to the invariant measure for configurational quantities) recently demonstrated in the setting of Langevin dynamics. Furthermore, we propose a covariance-controlled adaptive Langevin (CCAdL) thermostat that can effectively dissipate parameter-dependent noise while maintaining a desired target distribution. The proposed method achieves a substantial speedup over popular alternative schemes for large-scale machine learning applications.

Du fait de l'augmentation de la demande de produits pour les applications grand public, industrielles et automobiles, des mémoires embarquées fiables et à faible coût de fabrication sont de plus en plus demandées. Dans ce contexte, les mémoires split-gate à piégeage discret sont proposées pour des microcontrôleurs. Elles combinent l'avantage d'une couche de stockage discrète et de la con guration split-gate. Durant ce travail de recherche, des mémoires split-gate à couche de piégeage discret ayant des longueurs de grille de 20nm sont présentées pour la première fois. Celles-ci on été réalisées avec des nanocristaux de silicium (Si-nc), du nitrure de silicium (SiN) ou un hybride Si-nc/SiN avec diélectrique de control de type SiO2 ou AlO et sont comparées en termes de performances lors des procédures d'eff acement et de rétention. Ensuite, la miniaturisation des mémoires split-gate à piégeage de charge est étudié, en particulier au travers de l'impact de la réduction de la longueur de grille sur la fenêtre de mémorisation, la rétention et la consommation. Le rôle des défauts dans le diélectrique de contrôle (alumine) utilisé dans les mémoires de type TANOS a été étudié. Des travaux ont été menés pour déterminer l'origine des pièges dans ce matériau, par le biais de la simulation atomistique ainsi que d'analyses physico-chimiques précises. Nous avons montré que la concentration de pièges dans AlO pouvait être réduite par ajustement des conditions de procédé de fabrication, débouchant ainsi sur l'amélioration de la rétention dans les mémoires à piégeage de charge. Ce résultat est convenable pour les applications de type embarqué / Due to the increasing demand for consumer, industrial and automotive products, highly reliable, and low integration cost embedded memories are more and more required. In this context, split-gate charge trap memories were proposed for microcontroller products, combining the advantage of a discrete storage layer and of the split-gate con guration. In this thesis, split-gate charge trap memories with electrical gate length down to 20nm are presented for the 1st time. Silicon nanocristals (Si-nc), or silicon nitride (SiN) and hybrid Si-nc/SiN based split-gate memories, with SiO2 or AlO control dielectrics, are compared in terms of program erase and retention. Then, the scalability of split-gate charge trap memories is studied, investigating the impact of gate length reduction on the memory window, retention and consumption. We thus studied the role of defects on alumina control dielectric employed in TANOS-like memory. We used atomistic simulation, consolidated by a detailed alumina physico-chemical material analysis, to investigate the origin of traps in alumina. We showed that the trap concentration in AlO can be decreased by adjusting the process conditions leading to improved retention behaviour in charge trap memory, suitable for embedded applications.

Les alginates forment des gels transparents en solution aqueuse en présence de certains ions divalents. Cette propriété est principalement attribuée à la formation de zones de jonction impliquant les séquences (1->4)-a-L-guluronane de chaînes adjacentes. Des oligomères d'alginates ont été utilisés comme briques élémentaires pour la synthèse de polymères biohybrides contenant des chaines pendantes oligo-(1->4)-a-L-guluronane. La rhéologie et la diffusion de la lumière ont permis d'étudier leur gélification ionotropique. De plus, une image atomistique des associations entre chaines latérales a été donnée grâce à la modélisation moléculaire et la microscopie de force atomique. Les polymères biohybrides portant des résidus pendant (1->4)-a-L-guluronane forment des gels en présence de Ca2+. L'addition de blocs guluronane ou mannuronane au gel préformé fait diminuer sa force avec quasiment la même efficacité. L'étude par dynamique moléculaire de séquences (1->4)-a-L-guluronan totalement chargées en présence d'ions Ca2+ suggère qu'environ 8 unités de répétition sont suffisantes pour former spontanément des zones de jonction. De plus, l'analyse conformationnelle de duplexes de chaines (1->4)-a-L-guluronane ayant 12 unités de répétition révèle une grande variété de conformations accessibles, ce qui est consistant avec la difficulté d'obtention de cristaux de Ca2+-guluronate de dimension suffisante pour les études cristallographiques. Les forces d'adhésion entre des homo-oligomères d'alginates en présence de Ca2+ mesuré par spectroscopie de force atomique montrent que la force d'interaction croit selon l'ordre suivant: M-M < M-G or G-M < G-G. Un résultat important est que les blocs mannuronanes, en complexe avec le calcium, peuvent être impliqués dans des associations homotypiques et hétérotypiques. Ce résultat est consistant avec la détection d'agrégats d'oligomères de mannuronanes observés en diffusion de la lumière pendant l'addition de CaCl2. Les blocs M contribuent donc également à la formation du gel mais la force associée est plus faible que celle des blocs G. / Alginates form transparent hydrogels in aqueous solution upon addition of some divalent cations. This property is mostly due to the formation of junction zones involving (1->4)-a-L-guluronan sequences on adjacent polymer chains. Oligomers of alginates were used as molecular bricks for the synthesis of biohybrid polymers featuring (1->4)-a-L-guluronan sequences as side chains. Rheology and Light Scattering have been applied to investigate their ionotropic gelation. In addition, an atomistic picture of the Ca2+-driven side chain associations was also provided thanks to Molecular Modeling and Atomic Force Spectroscopy. Biohybrid polymers carrying (1->4)-a-L-guluronan residues formed soft and transparent hydrogels in the presence of Ca2+. The addition of either guluronan, or mannuronan blocks to the pre-formed gel reduced its strength almost with the same efficiency. A molecular dynamics investigation of fully charged (1->4)-a-L-guluronan sequences in the presence of a neutralizing amount of Ca2+ ions suggested that about 8 repeating units may be sufficient to the spontaneous formation of junction zones. Furthermore, conformational analysis of (1->4)-a-L-guluronan chain having 12 repeating units in duplexes revealed a wide variety of accessible conformations, a feature consistent with the general difficulty in obtaining crystals of Ca2+-guluronate with suitable lateral dimensions for crystallographic studies. The adhesion forces between homo-alginate oligomers in the presence of Ca2+ measured by Atomic Force Spectroscopy showed that the strength of interactions increased in the following order: M-M < M-G or G-M < G-G. One of the most significant findings to emerge from this study is that mannuronan blocks complexed via calcium ions can be involved in both homotypic and heterotypic associations. This result is consistent with the detection of aggregates observed for mannuronan oligomers by Light Scattering during the addition of CaCl2. Thus, M-blocks also contribute to the gel formation but their strength seemed to be however weaker than G-blocks.

Submitted by Luciana Sebin (lusebin@ufscar.br) on 2016-09-14T18:11:05Z No. of bitstreams: 1 DissMF.pdf: 4470180 bytes, checksum: 46b46e581cf95360c3fc86808b84e68a (MD5) / Approved for entry into archive by Marina Freitas (marinapf@ufscar.br) on 2016-09-15T14:01:26Z (GMT) No. of bitstreams: 1 DissMF.pdf: 4470180 bytes, checksum: 46b46e581cf95360c3fc86808b84e68a (MD5) / Approved for entry into archive by Marina Freitas (marinapf@ufscar.br) on 2016-09-15T14:01:30Z (GMT) No. of bitstreams: 1 DissMF.pdf: 4470180 bytes, checksum: 46b46e581cf95360c3fc86808b84e68a (MD5) / Made available in DSpace on 2016-09-15T14:01:38Z (GMT). No. of bitstreams: 1 DissMF.pdf: 4470180 bytes, checksum: 46b46e581cf95360c3fc86808b84e68a (MD5) Previous issue date: 2015-12-17 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / This work presents an experience directed on the construction, development and implementation of a playful activity in the Teaching of Chemistry, with students of the first year of high school State School "Captain Agenor de Carvalho" in the municipality of Estiva Gerbi, State of São Paulo in Brazil. This experience has been a digital board game and given, involving questions of Chemistry, with contents of Atomistic. The game is available on the internet at Portal Education under the name of “Ludo Atomistic”. The game was applied in the computer room of the school, through the system Accesses School during the class of Chemistry. Students were evaluated through a tool in the portal with all information for analysis of hits and errors of the issues, access and frequency. It was as analyzed the performance of students in the classroom, their interests in the contents and their participation in activities in school and in their homes. The idea was to get an attractive and innovative, enjoyable and interesting methodology for teaching. The game Ludo Atomistic demonstrated collaborate in the process of teaching and learning, in a differentiated, attractive and dynamic manner, because with didactic-pedagogical purpose promoted beyond pleasure and fun, the construction of knowledge, to connect various aspects of the learning process as cognition, affection, socialization and creativity. / O presente trabalho apresenta uma experiência direcionada na construção, elaboração e aplicação de uma atividade lúdica no ensino de Química, com alunos do 1º Ano do Ensino Médio da Escola Estadual “Capitão Agenor de Carvalho” no município de Estiva Gerbi, estado de São Paulo. Nesta experiência foi desenvolvido um jogo digital com tabuleiro e dado, envolvendo perguntas da disciplina de Química, dos conteúdos de Atomística. O jogo está disponível na internet no Portal Ludo Educativo com o nome de Ludo Atomística. Foi aplicado na sala de informática da escola, através do sistema Acessa Escola durante as aulas de Química. Os alunos foram avaliados através de uma ferramenta disponível no portal, com todas as informações para análise de acertos e erros das questões, frequências de acessos e os seus rendimentos. Também foi analisado o desempenho dos alunos em sala de aula, seus interesses nos conteúdos e suas participações nas atividades desenvolvidas na escola e em suas casas. A ideia foi buscar uma metodologia inovadora e atraente para ensinar de forma mais prazerosa e interessante. O jogo Ludo Atomística demostrou colaborar no processo de ensino e aprendizagem, de forma diferenciada, dinâmica e atrativa, pois com finalidade didático-pedagógica promoveu além de prazer e divertimento, a construção do conhecimento, ao conectar vários aspectos do processo de aprendizagem, como cognição, afeição, socialização e criatividade.

Shape memory alloys (SMAs) are materials that show reversible, thermo-elastic, diffusionless, displacive (solid to solid) phase transformation, due to the application of temperature and/ or stress (/strain). Among different SMAs, NiTi is a popular one. NiTi shows reversible phase transformation, the shape memory effect (SME), where irreversible deformations are recovered upon heating, and superelasticity (SE), where large strains imposed at high enough temperatures are fully recovered. Phase transformation process in NiTi SMA is a very complex process that involves the competition between developed internal strain and phonon dispersion instability. In NiTi SMA, phase transformation occurs over a wide range of temperature and/ or stress (strain) which involves, evolution of different crystalline phases (cubic austenite i.e. B2, different monoclinic variant of martensite i.e. B19', and orthorhombic B19 or BCO structures). Further, it is observed from experimental and computational studies that the evolution kinetics and growth rate of different phases in NiTi SMA vary significantly over a wide spectrum of spatio-temporal scales, especially with length scales. At nano-meter length scale, phase transformation temperatures, critical transformation stress (or strain) and phase fraction evolution change significantly with sample or simulation cell size and grain size. Even, below a critical length scale, the phase transformation process stops. All these aspects make NiTi SMA very interesting to the science and engineering research community and in this context, the present focuses on the following aspects. At first this study address the stability, evolution and growth kinetics of different phases (B2 and variants of B19'), at different length scales, starting from the atomic level and ending at the continuum macroscopic level. The effects of simulation cell size, grain size, and presence of free surface and grain boundary on the phase transformation process (transformation temperature, phase fraction evolution kinetics due to temperature) are also demonstrated herein. Next, to couple and transfer the statistical information of length scale dependent phase transformation process, multiscale/ multiphysics methods are used. Here, the computational difficulty from the fact that the representative governing equations (i.e. different sub-methods such as molecular dynamics simulations, phase field simulations and continuum level constitutive/ material models) are only valid or can be implemented over a range of spatiotemporal scales. Therefore, in the present study, a wavelet based multiscale coupling method is used, where simulation results (phase fraction evolution kinetics) from different sub-methods are linked via concurrent multiscale coupling fashion. Finally, these multiscale/ multiphysics simulation results are used to develop/ modify the macro/ continuum scale thermo-mechanical constitutive relations for NiTi SMA. Finally, the improved material model is used to model new devices, such as thermal diodes and smart dampers.

Notre étude concerne la simulation atomistique des interactions à la fois au sein et entre les nanoparticules d’or. Nous avons d’abord examiné l’organisation des molécules d’alcanethiol, avec différentes longueurs de chaînes alkyles, sur la surface des nanocristaux (NCs) d’or de tailles et de formes différentes. Ainsi, pour des NCs d’or d’une taille allant de 1 à 10 nm et quel que soit le type d’alcanethiol, nous avons montré que contrairement aux NCs de forme cubique qui ne présentent qu’une seule organisation moléculaire, les NCs de forme octaédrique et icosaédrique présentent deux organisations moléculaires différentes: une sur les bords et l’autre au centre des facettes. De plus, le taux de couverture de surface dépend très peu de la forme et de la taille des NCs ainsi que de la longueur des chaînes d’alcanethiols. Néanmoins, grâce à l’organisation compacte des molécules d’alcanethiol sur les bords des NCs, ce taux de couverture reste plus important que celui des surfaces planes d’or. Nous avons également mis au point un modèle théorique pour estimer ce taux de couverture dans le cas de NCs icosaédriques d’une taille bien supérieure à 10 nm. On a montré que pour des NCs d’une taille comprise entre 10 et 20 nm, le taux de couverture prédit par notre modèle est en bon accord avec de récentes données expérimentales. On a aussi démontré que pour obtenir le taux de couverture observé sur les surfaces planes d’or, il faut des NCs d’une taille supérieure à 100 nm. Dans un second temps, les interactions entre les NCs au sein de réseaux supracristallins organisés, appelés supracristaux, ont été analysées. Nous avons alors mis en évidence que ces interactions sont influencées par le rapport entre la longueur des chaînes alkyles et la taille des NCs, en bon accord avec la théorie des cônes superposés et avec les données expérimentales. Dans la continuité de ce travail, la prise en compte du solvant s’avère aussi importante pour comprendre davantage les interactions entre les NCs d’or. / Our study concerns the atomistic simulations of interactions within and between gold nanocrystals (NCs). We first examined the molecular organization of several alkanethiol molecules adsorbed on gold NCs with different size and shape. Thus, for 1 to 10 nm sized NCs, we have shown that unlike cubic shaped NCs which have only one molecular organization, octahedral and icosahedral shaped NCs present two different molecular organizations, one on the edges and the other one in the centers of their facets. Moreover, the surface coverage ratio depends very slightly on the shape and size of the NCs and also on the length of the alkanethiol chain. Nevertheless, thanks to the dense molecular organization of thiols on the NC edges, this coverage ratio remains higher than for flat gold surfaces. We have also developed a theoretical model to estimate the surface coverage for icosahedral shaped NCs larger than 10 nm. It has been shown that for NCs between 10 and 20 nm, the surface coverage predicted by our model is in good agreement with recent experimental data. We also found that it takes NCs bigger than 100 nm to match the surface coverage of flat gold surfaces. Then, the interactions between NCs in organized supracrystalline lattices, called supracrystals, were analyzed. We have shown that these interactions are influenced by the ratio between the length of the alkyl chains and the size of the NCs, in good agreement with the Overlap Cone Model and experimental data. In prospects, solvent consideration could be important for further understanding of gold NCs interactions.

Adverse changes in the Earth's climate are thought to be due to the output of carbon dioxide from power stations. This has led to the development of many new materials to remove CO2 from these gas streams. Polymers of intrinsic microporosity (PIMs) are a novel class of polymers that are rigid with sites of contortion. These properties result in inefficient packing and so lead to large pore volumes and high surface areas. The inclusion of Tröger’s base, a contortion site made up of two nitrogen atoms, is thought to lead to increased uptake of CO2. The combination of electrostatic interactions with strong van der Waals forces should interact favourable with the quadrupole moment of CO2.Here a molecular simulation study of a selection of these polymers is presented. The study begins by developing a quick screening method on single polymer chains. This shows that the high surface area and adsorption affinity are a result of the contorted nature of PIMs along with the inclusion of groups such as Tröger’s base.The creation of atomistic models that reproduce the space packing ability of these polymers is also explored. Methods developed for PIMs in literature are investigated along with a new method developed during this study. GCMC simulations are then used to investigate the adsorption of CO2. In this study it is seen that that these polymers possess a well percolated network of both ultramicropores and supermicropores with a significant fraction of these pores being close to the kinetic diameter of CO 2. It is posited that these pores may be the result of the inclusion of Tröger’s base. It is also shown that this produces a particularly favourable site for adsorption. The phenomenon of swelling as a result of CO2 adsorption is also investigated using a variety of methods that make use of the output from the GCMC simulations. It was found that swelling is negligible for pressures of up to 1 bar. This result is important as swelling in the polymer can lead to a reduction in selectivity and an increase in permeability, which can affect the overall material’s performance.