Dissertations / Theses on the topic 'Grand Canonical Monte Carlo simulations'

The purpose of the work is to employ molecular simulation to further extend the understanding of Self-Assembled Monolayers (SAMs), especially as it relates to three particular applications: organic-inorganic composite membranes, surface treatments in Micro-Electro-Mechanical Systems (MEMS) and organic-surface-modified Ordered Mesoporous Materials (OMMs). The first focus area for the work is the use of SAMS in organic-inorganic composite membranes for gas separations. These composite membranes, recently proposed in the literature, are based on the chemical derivatization of porous inorganic surfaces with organic oligomers. Our simulations achieve good qualitative agreement with experiment in several respects, including the improvement in the overall selectivity of the membrane and decrease in the permeance when increasing the chain length. The best improvement in the overall solubility selectivity is reached when the chains span throughout the pore. The second application focus is on the use of SAMs as coatings in MEMS devices. The work focuses on the modeling of adhesion issues for SAM coatings at the molecular level. It is shown that as the chain length is increased from 4 to 18 carbon atoms, the adhesion forces between two monolayers at the same separations decreases. The third application focus is on the use of SAMs for tailoring surface and structural properties of OMMs, in particular, porous silicas. A molecular study of structural and surface properties of a silica material with a 5 nm pore size, modified via chemical bonding of organosilanes with a range of sizes (C4, C8 and C18) is presented. Grand canonical MC simulations are employed to obtain nitrogen adsorption isotherms for unmodified and modified MCM-41 material models. Furthermore, the density profiles of alkyl chains and nitrogen molecules are analyzed to clarify the differences in the adsorption mechanisms in unmodified and modified materials. The position of the capillary condensation steps gradually shifted to lower pressure values with the increase in size of the bonded ligands, and this shift was accompanied by a gradual disappearance of the hysteresis loop. As the length of the bonded ligands is increased, a systematic decrease in the pore diameter is observed and the multi-layer adsorption mechanism in modified model materials diminishes.

Dissertação para obtenção do Grau de Doutor em Engenharia Química
FCT - PhD Fellowship at Universidade Nova de Lisboa, Department of Chemistry (bolsa N SFRH/BD/45477/2008); FCT Program, project PTDC/AAC-AMB/108849/2008; NANO_GUARD, Project N°269138; Programme “PEOPLE” – Call ID “FP7-PEOPLE-2010-IRSES”

In recent years, metal-organic frameworks (MOFs) have been identified as promising adsorbents in a number of industrially relevant, yet challenging, separations, including the removal of propane from propane/propylene mixtures and the separation of mixtures of xylene isomers. The highly tuneable nature of MOFs - wherein structures may be constructed from a variety of diverse building blocks – has resulted in the publication of a staggering number of frameworks incorporating a wide range of network topologies, pore shapes and pore diameters. As a result, there are a huge number of candidate adsorbents to consider for a given separation. Molecular simulation techniques allow the identification of those structural features and characteristics of a MOF which exert the greatest influence on the adsorption and separation of the compounds of interest, providing insights which can both guide the selection and accelerate the development of adsorbents for a specific application. The separation of propane/propylene mixtures via adsorption has typically focused on selective adsorption of the olefin, propylene, via specific olefin-adsorbent interactions. These propylene-selective MOFs result in processes which selectively remove the most abundant species in the process stream and are typically characterised by high heats of adsorption, resulting in large adsorption units and adsorbents which are difficult to regenerate. In this work, the capability of MOFs to selectively adsorb propane over propylene is explored, potentially allowing for the design of smaller and more energy-efficient adsorption units. By studying a range of different MOFs as well as carbon-based model pores, it was found that the low-pressure selectivity of the structure is determined by the strength of the electrostatic interaction between propylene and the framework, while the adsorptive preference at industrially-relevant pressures is dominated by the enhanced packing efficiency of propylene over propane. The confinement of C3 molecules, however, may be employed to negate this entropic advantage and guide the development of materials which selectively adsorb propane over propylene. It has recently been reported that the adsorptive preference of a MOF for one xylene isomer over another may be predicted based solely on the pore size distribution of the structure. In this work, the impact of pore size on selectivity was studied systematically in both one-dimensional model pore systems of varying geometries and analogous published MOF structures. The ability of the framework to discriminate between xylene molecules in these systems was found to be determined primarily by the different packing arrangements available to the different isomers – while small pores were found to favour the slimmest of the isomers, larger pores were found to favour the more compact ortho- isomer. Finally, the adsorption and diffusion of xylene isomers in a more complex MOF, UiO-66(Zr), was studied in depth. Simulations were able to correctly predict the previously-reported preference of the MOF for ortho-xylene (oX). The smaller volume of the oX molecule compared to the other isomers was found to be responsible both for an enhanced entropic contribution and higher guest-host interaction energies. The importance of framework flexibility in the diffusion of xylene isomers in UiO-66(Zr) was also explored, with distortion of the structure in response to interaction with adsorbed molecules found to be essential in allowing xylenes to diffuse through the pore space.

Metal--organic frameworks (MOFs) are porous crystalline materials that are synthesized from rigid organic ligands and metal-containing clusters. They are highly tunable as a number of different structures can be made by simply changing the organic ligand and/or metal ion. MOFs are a promising class of materials for many energy-related applications, including H2 storage and CO2 capture and sequestration. Computational studies can provide insights into MOFs and the mechanism of gas sorption and separation. Theoretical studies on existing MOFs are performed to determine what structural characteristics leads to favorable gas sorption mechanisms. The results from these studies can provide insights into designing new MOFs that are tailored for specific applications. In this work, grand canonical Monte Carlo (GCMC) simulations were performed in various MOFs to understand the gas sorption mechanisms and identify the favorable sorption sites in the respective materials. Experimental observables such as sorption isotherms and associated isosteric heat of adsorption, Qst, values can be generated using this method. Outstanding agreement with experimental measurements engenders confidence in a variety of molecular level predictions. Explicit many-body polarization effects were shown to be important for the modeling of gas sorption in highly charged/polar MOFs that contain open-metal sites. Indeed, this was demonstrated through a series of simulation studies in various MOFs with rht topology that contain such sites. Specifically, the inclusion of many-body polarization interactions was essential to reproduce the experimentally observed sorption isotherms and Qst values and capture the binding of sorbate molecules onto the open-metal sites in these MOFs. This work also presents computational studies on a family of pillared square grid that are water-stable and display high CO2 sorption and selectivity. These MOFs are deemed promising for industrial applications and CO2 separations. Simulations in these materials revealed favorable interactions between the CO2 molecules and the SiF62- pillars. Further, the compound with the smallest pore size exhibits the highest selectivity for CO2 as demonstrated through both experimental and theoretical studies. Many other MOFs with intriguing sorption properties are investigated in this work and their sorption mechanisms have been discerned through molecular simulation.

This research builds up a multiphysics molecular model for nano electromechanical contact switch in a gaseous environment. To predict the device dynamic properties precisely, multiple methods have been incorporated, including: grand canonical Monte Carlo method for adsorption phenomenon, atomistic moment theory for dynamic electric field, and molecular dynamic simulation for carbon nanotube deformation. Using such a model, the charge distribution has been characterized; the adsorption influence on the frequency change and damping ratio has been investigated. The model has a great potential in the future design of nano electromechanical system.

La simulación molecular presenta la ventaja de ofrecer un marco teórico importante para predecir propiedades termodinámicas y de transporte de fluidos con aplicaciones industriales. En este trabajo, se explotó está ventaja para predecir el equilibrio líquido vapor de agua, compuestos aromáticos y sus mezclas a condiciones tanto sub- como supercríticas. Se realizó una comparación de diferentes potenciales intermoleculares conocidos mediante el cálculo de propiedades termodinámicas de sistemas puros que sirvió de punto de partida para llevar a cabo una optimización de parámetros transferibles para un potencial intermolecular de agua y compuestos aromáticos. En el caso de agua, se llevo a cabo el análisis y evaluación de propiedades termodinámicas de un modelo simple de agua. En este modelo, las contribuciones electrostáticas se aproximan mediante interacciones de corto alcance en vez de las típicas fuerzas de Coulomb de largo alcance. En general, se han encontrado grandes desviaciones con respecto a los datos experimentales, tal como un valor de temperatura crítica de 360K, valor 50% alejado del valor experimental. Debido a que estos resultados nos indican la importancia de incluir las fuerzas de Coulomb en el modelo molecular empleado para reproducir correctamente las propiedades de agua, el trabajo de investigación se ha enfocado en la optimización de los parámetros de los potenciales TIP4P y SPC/E. Los resultados obtenidos muestran que es posible encontrar una mejor aproximación al punto crítico experimental a partir de la optimización del modelo SPC/E. Sin embargo, el buen acuerdo con los experimentos del modelo original a condiciones ambiente se pierde usando los parámetros del modelo optimizado. Por otro lado, la estimación de propiedades de compuestos aromáticos esta de acuerdo con los datos experimentales permitiendo la reproducción de la densidad de líquido saturado, presión de saturación y entalpía de vaporización para compuestos puros. Finalmente, en el caso de mezclas se ha aplicado el conjunto de parámetros obtenidos para aromáticos. Las propiedades termodinámicas de la mezcla binaria aromático-aromático y aromático agua son analizadas en un amplio rango de temperaturas y presiones. Las desviaciones encontradas entre los valores calculados y los experimentales sugieren aplicar un mejor método de optimización para sistemas puros o por otro lado, promover un potencial de interacción intermolecular más sofisticado. Las estimaciones a condiciones cercanas al punto crítico están en buen acuerdo con los datos experimentales.
La simulació molecular presenta l'avantatge d'oferir un marc teòric important per a cercar propietats termodinàmiques i de transport de fluids amb aplicacions industrials. En aquest treball es va explotar aquesta avantatge per predir l'equilibri líquid vapor d'aigua, components aromàtics i les seves mescles, tant a condicions sub com supercrítiques. Es va realitzar una comparació de diferents potencials intermoleculars, coneguts mitjançant el càlcul de propietats termodinàmiques de sistemes purs, que ha servit de punt de sortida per portar a terme una optimització de paràmetres transferibles per a un potencial intermolecular de propietats termodinàmiques d'un model simple d'aigua. En aquest model, les contribucions electrostàtiques s'aproximen mitjançant interaccions de curt abast en lloc de les típiques forces de Coulomb de llarg abast. En general, s'ha trobat grans desviacions respecte a les dades experimentals, tal com un valor de temperatura crítica de 360K, valor 50% allunyat del valor experimental. Degut a que aquests resultats ens indiquen la importància d'incloure les forces de Coulomb en el model molecular emprat per reproduir correctament les propietats d'aigua, el treball d'investigació s'ha enfocat en l'optimització dels paràmetres dels potencials TIP4P i SPC/E. Els resultats obtinguts mostren que és possible trobar una millor aproximació al punt crític experimental a partir de l'optimització del model SPC/E. No obstant, el bon acord amb els experiments del model original a condicions ambientals es perden usant els paràmetres del model optimitzat. Per altre banda, l'estimació de propietats de compostos aromàtics esta d'acord amb les dades experimentals permetent la reproducció de la densitat de líquid saturat, pressió de saturació i entalpia de vaporització per a compostos purs mitjançant el potencial AUA-Aromátics proposat. Finalment, en el cas de mescles s'ha aplicat el conjunt de paràmetres obtinguts per aromàtics. Les propietats termodinàmiques de la mescla binària aromàtic-aromàtic i aromàtic-aigua són analitzades en un ample rang de temperatures i pressions. Les desviacions trobades entre els valors calculats i els experimentals suggereixen aplicar un millor mètode d'optimització per a sistemes purs o, per altre banda, promoure un potencial d'interacció intermolecular més sofisticat. Les estimacions en condicions properes al punt crític tenen un bon acord amb les dades experimentals.
Molecular simulation presents the advantage of providing a unified theoretical framework to model fluid properties for industrial applications. In this work we exploit this advantage to predict thermodynamic properties of pure water and aromatics and their mixtures at sub- and supercritical conditions. A comprehensive comparison of different intermolecular potentials has been carried out in order to analyze model predictions for pure component properties. In addition, an optimization of transferable parameters has been performed for an intermolecular potential for aromatics and water. In the case of water, an analysis and evaluation of the thermodynamic properties of a simple model has been performed. In this model, the electrostatic contributions are approximated by short-range interactions instead of the typical long-range Coulombic forces. On the whole, we found huge deviations with experimental data, such as a critical temperature value of 360K, 50% far away from the experimental value. Since, these calculations indicate the importance of including the electrostatic contribution in order to correctly model water, we also focus on reproducing critical properties from an optimization of the well known TIP4P and SPC/E water model parameters. Results obtained show that a better approximation to the critical point prediction is possible from the optimization of the SPC/E parameters, however, the good agreement with experiments for the original model at room conditions vanishes using the optimized parameters. On the other hand, thermodynamic property estimations of aromatic molecules are in good agreement with experimental data and we are able to reproduce saturation liquid densities, saturation pressures, vaporization enthalpies and liquid structure for pure compounds. Finally, in the case of mixtures, we applied the optimized set of parameters obtained for aromatics. The thermodynamic properties of binary aromatic-aromatic and aromatic water mixtures are analyzed over a wide range of temperatures and pressures. Deviations between the predicted and experimental values are found at low temperatures and high densities suggesting that a better optimization process needs to be performed for the pure systems or a more sophisticated intermolecular interaction potential is needed. Nevertheless, the estimations close to critical conditions are in good agreement with experimental data.

Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Chemical Engineering, 2007.
Includes bibliographical references.
Understanding the structure of materials, and how this structure affects their properties, is an important step towards the understanding that is necessary in order to apply computational methods to the end of designing materials to fit very specific needs. Such needs include specific optical and mechanical properties. In polymers, the ability to easily create orientation through a variety of processes allows the production of materials that, while chemically similar, exhibit a wide variety of optical and mechanical properties. The ability to illuminate the connections between structure and optical or mechanical properties depends on the ability to reliably interpret a wide variety of experimental measurements. I assert that thermodynamic consistency and energy minimization is an integral part of this endeavor; reliable analyses of structure and properties are built upon the foundation of a minimum-free-energy ensemble of configurations that reproduces the experimental results. This project encompasses three goals, which make up this thesis: 1) to show how sets of experimental measurements are integrated into simulations to produce thermodynamically consistent, minimum-free-energy ensembles; 2) to show how these ensembles can characterize the conformations of macromolecules, which are not available from direct simulation; 3) to show how dynamic processes, which create inhomogeneous systems can be incorporated, along with experimental structural measurements, into thermodynamically consistent, minimum-free-energy ensembles. To achieve the first of these goals, we describe the application of the Semi-Grand Canonical Monte Carlo (SGMC) method to analyze and interpret experimental data for non-equilibrium polymer melts and glasses. Experiments that provide information about atomic-level ordering, e.g. birefringence, are amenable to this approach.
(cont.) Closure of the inverse problem of determining the structural detail from limited data is achieved by selecting the lowest-free-energy ensemble of configurations that reproduces the experimental data. The free energy is calculated using the thermodynamic potential of the appropriate semi-grand canonical (SGC) ensemble ... , as defined by the experimental data. To illustrate the method we examine uniaxially oriented polyethylene melts of average chain length up to C400. The simulation results are analyzed for features not explicitly measured by birefringence, such as the density, torsion angle distribution, molecular scale orientation and free energy, to understand more fully the underlying features of these non-equilibrium states. The stress-optical rule for polyethylene is evaluated in this way. The second goal is achieved through multi-scale modeling, which requires the selection and preservation of information crucial to understanding the behavior of a system at appropriate length and time scales. For a description of processed polymers, such a model must successfully link rheological properties with atomic-level structure. We propose a method for the calculation of an important rheological state descriptor, the configuration tensor , from atomistic simulations of oligomers. The method requires no adjustable parameters and can describe anisotropic polymer conformations at conditions of significant deformation. We establish the validity of the atomistic-to-macromolecular scaling by comparing the consistency of macromolecular predictions of among different polyethylene (PE) oligomer systems. We use this method with the previously reported Semi-Grand Canonical Monte Carlo (SGMC) method to deduce macromolecular and atomic-level structural information interchangeably for systems with flow-induced orientation. Introducing the ability to model arbitrary points in a dynamic process fulfills the third goal elaborated above.
(cont.) Because the characteristic relaxation times of processed polymer chains often span several orders of magnitude, it is commonly the case that partial relaxation of the chains is frozen into the final product. We report results of molecular simulations by the Semi-grand Canonical Monte Carlo (SGMC) method to study the orientation-dependent elasticity of glassy polystyrene as a function of both the system-average degree of orientation and the degree of relaxation of chain ends at a constant average degree of orientation, in accord with the tube model of Doi and Edwards. Our simulations reproduce quantitatively the experimentally observed changes in the tensile modulus E33 as a function of both average orientation and inhomogeneity of the orientation due to partial relaxation. The results show that the partial relaxation of the polymer chains is sufficient to explain the observed variation of mechanical properties for samples that differ in processing history, yet have the same observed birefringence.
by Frederick E. Bernardin, III.
Ph.D.

Orientadores: Munir Salomão Skaf, Vitor Rafael Coluci
Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Química
Made available in DSpace on 2018-08-26T20:42:42Z (GMT). No. of bitstreams: 1 Faro_TatianaMellodaCosta_D.pdf: 8054394 bytes, checksum: ce0d79df42ce453ffc39b51bf0ad1094 (MD5) Previous issue date: 2015
Resumo: Atualmente, a economia mundial depende do uso de combustíveis fósseis para a geração de energia. Esse modelo apresenta problemas ambientais graves, uma vez que o petróleo é um material não-renovável e muito poluente. O gás hidrogênio apresenta-se como uma alternativa promissora para substituir os combustíveis utilizados atualmente devido a um conjunto de características positivas: ele é atóxico, tem uma alta densidade energética gravimétrica e gera apenas água como produto de sua combustão. Apesar de tais vantagens, ele ainda não é utilizado comercialmente em larga escala. O maior empecilho tecnológico para que o hidrogênio possa substituir os combustíveis fósseis está no seu armazenamento. Existem diversas propostas para armazenar o hidrogênio, como tanques contendo o hidrogênio nas formas de gás pressurizado ou de líquido, além de sistemas sólidos que permitam a sua adsorção. Todavia, nenhum sistema construído até então foi capaz de armazenar o hidrogênio de forma tão barata, segura e eficaz quanto seria necessário. Nanoestruturas de carbono são vistas como uma boa alternativa para construir dispositivos de armazenamento de hidrogênio baseados na fisissorção. Os nanopapiros de carbono, formados por folhas de grafeno enroladas no formato de um papiro, são considerados particularmente promissores para armazenar o hidrogênio, uma vez que possuem uma alta área superficial, extremidades abertas e distâncias intercamadas facilmente controláveis. Na primeira etapa deste trabalho, realizamos simulações de Dinâmica Molecular (MD) para estudar a dinâmica e a estabilidade de diversos nanopapiros em função de alguns dos seus parâmetros estruturais. Posteriormente, aplicamos o método de Monte Carlo Grand-Canônico (GCMC) para estudar o processo de adsorção de hidrogênio em nanopapiros selecionados, de forma a caracterizar quantitativamente e qualitativamente as fases adsorvidas
Abstract: Presently, the world economy depends on the use of fossil fuels to generate energy. This model presents serious environmental problems, since petroleum is a non-renewable and very pollutant material. Hydrogen gas presents itself as a promising alternative to substitute the fuels currently used due to a few positive characteristics: it is non-toxic, possesses a high gravimetric energetic density and only generates water as a combustion byproduct. In spite of all these advantages, hydrogen still isn't used commercially in a large scale. The biggest technological drawback for hydrogen to substitute fossil fuels is in its storage. There are many proposed ways to store hydrogen, such as tanks containing highly pressurized or liquid hydrogen, or solid systems that allow its adsorption. However, no system built up to the date had been able to store hydrogen as cheap, safe and efficiently as necessary. Carbon nanostructures are seen as a good alternative to build hydrogen storage devices based on physisorption. Carbon nanoscrolls, formed by graphene sheets scrolled in a papirus-like shape, are considered as particularly promising adsorption materials, since they possess a high surface area, open edges and easily controllable interlayer distances. In the first step of this work, we made Molecular Dynamics (MD) simulations to study the dynamics and the stability of several nanoscrolls as a function of their structural parameters. Subsequently, we used the Grand-Canonical Monte Carlo (GCMC) method to study the hydrogen adsorption process in selected nanoscrolls, as to characterize the adsorbed phases quantitatively and qualitatively
Doutorado
Físico-Química
Doutora em Ciências

La premie§re partie de cette the§se est centre§e sur la mission ECLAIRs, de§die§e a§ l'e§tude de l'e§mission prompte multi-longueurs d'onde des sursauts. Les performances de la came§ra X ⇋đ d'imagerie grand champ d'ECLAIRs sont estime§es par des simulations Monte-Carlo. La sensibilite§ de de§tection des sursauts de§pend principalement du bruit de fond sur la came§ra. En prenant en compte les principales composantes de l'environnement spatial (le diffus X extragalactique, les protons du rayonnement cosmique et atmosphe§riques, les neutrons atmosphe§riques, et les photons X-⇋đ de l'albe§do terrestre) pour une orbite d'ECLAIRs a§ 600 km d'altitude et a§ 20o d'inclinaison, le bruit de fond dans la bande d'imagerie de 4 a§ 50 keV est estime§ a§ 7,1 coups cm-2 s-1. La sensibilite§ limite pour un seuil de de§tection de 5,5 ≥ des fluctuations du bruit de fond est estime§e a§ 530 milli Crabe sur une seconde d'inte§gration dans la bande d'e§nergie de 4 a§ 50 keV. Compte tenu des niveaux de bruit de fond, le taux de sursauts de§tectables par an, dans la bande 4-300 keV, est estime§ entre 50 et 90 sursauts suivant la durete§ du sursaut. Pour un e§chantillon d'une centaine de sursauts de§tecte§s, 47% seront localise§s a§ mieux que 10 minutes d'arc et 61% a§ mieux 20 minutes d'arc pour un temps d'inte§gration de 1,024 secondes. Par ailleurs, avec un champ de vue de 105o x 105o et une sensibilite§ limite de 10 milli Crabe sur 10 h d'inte§gration dans la bande 20-200 keV et 3 milli Crabe dans la bande 4-10 keV, la came§ra X-⇋đ fera e§galement un balayage de la sphe§re ce§leste, a§ la recherche de noyaux actifs de galaxies, de novae X, et de Soft Gamma Repeaters. Dans la seconde partie de cette the§se, nous nous inte§ressons a§ l'apport du code de photo-ionisation, Titan, dans l'interpre§tation des spectres de haute re§solution des noyaux actifs de galaxies (NAG), obtenus en X avec les satellites XMM-Newton et Chandra. Nous montrons que les formalismes approche§s utilise§s pour re§soudre le transfert radiatif induisent des interpre§tations impre§cises des spectres des NAG en X, car les flux de raies calcule§es (notamment les raies de re§sonance) sont syste§matiquement surestime§s par 30% pour des milieux avec une densite§ de colonne totale CD < 1021 cm-2 a§ un ordre de grandeur pour des milieux avec CD > 1024 cm-2. A partir d'une e§tude the§orique du triplet de raies des ions he§liumoi§˜des, nous mettons e§galement en e§vidence un jeu de diagnostics spectroscopiques. Ces diagnostics permettent de de§terminer la densite§, la densite§ de colonne totale et le parame§tre d'ionisation des milieux photo-ionise§s observe§s, a§ partir de la mesure des flux de raies et de la tempe§rature des continus de recombinaison radiative.

Carbonaceous engine deposits tend to accumulate on most of the inner surfaces of the car engine. The presence of these deposits leads to a deteriorated efficiency of the engine and a number of adverse effects, such as higher propensity of the engine to knock. It has been proposed that selective adsorption of some of the fuel components in the porous deposits (and changing composition of the pre-combustion fuel) could be a contributing mechanism of the diminished efficiency of the engine. This, as well as other mechanisms of the deposits action, crucially depend on the porous structure of the material. Therefore, the aim of this investigation is to develop a method, which is able to accurately characterize the internal porous structure of the engine deposits and predict their adsorption properties at different conditions. This should allow us to assess whether the selective adsorption of fuel components is indeed a plausible contributing mechanism to the diminished performance of the engine. Accurate characterization of the engine deposits faces several difficulties due to their complex porous structure and chemical composition. A widely adopted approach in the characterization of activated carbons, which combines molecular simulation, specifically grand canonical Monte Carlo (GCMC) in slit pores, and experimental adsorption isotherms, is the starting point for the method suggested in this work. In this thesis, we will demonstrate that, by systematic modification of the solid-fluid interaction in the molecular simulation, we are able to correctly account for the chemical structural heterogeneity of the samples used. The new parameters of solid-fluid interaction allow us to extract representative pore size distributions and investigate the adsorption properties under different conditions of temperature and pressure, based on the obtained pore size distribution. Specifically, using the experimental data from a single ethane isotherm at 278K we accurately predict ethane adsorption at other temperatures and in different samples. Additionally, the proposed method is able to predict the adsorption of more complex hydrocarbons, i.e. n-butane and isobutane. The performance of the method is assessed by comparing the simulations results with the experimental adsorption measurements data on the engine deposits samples. Another important capability of the method is that it enables us to generate adsorption predictions of two key components commonly used to represent the combustion properties of the fuel, n-heptane and isooctane. We explore the equilibrium adsorption properties of these components based on the determined pore size distributions of the deposit samples. The results presented in the thesis highlight the importance of the adsorption in the internal porous structure of the engine deposits. The present study reinforces the value of molecular simulation combined with a limited number of experimental measurements, to accurately characterize heterogeneous carbonaceous materials and to make predictions at different conditions with sufficient precision.

Ziel dieser Arbeit ist zunächst die Entwicklung einer Vergleichsgrundlage, auf Basis derer Algorithmen zur Berechnung der Zustandsdichte verglichen werden können. Darauf aufbauend wird ein bestehendes übergangsmatrixbasiertes Verfahren für das großkanonisch Ensemble um ein neues Auswerteverfahren erweitert. Dazu werden numerische Untersuchungen verschiedener Monte-Carlo-Algorithmen zur Berechnung der Zustandsdichte durchgeführt. Das Hauptaugenmerk liegt dabei auf Verfahren, die auf Übergangsmatrizen basieren, sowie auf dem Verfahren von Wang und Landau. Im ersten Teil der Forschungsarbeit wird ein umfassender Überblick über Monte-Carlo-Methoden und Auswerteverfahren zur Bestimmung der Zustandsdichte sowie über verwandte Verfahren gegeben. Außerdem werden verschiedene Methoden zur Berechnung der Zustandsdichte aus Übergangsmatrizen vorgestellt und diskutiert. Im zweiten Teil der Arbeit wird eine neue Vergleichsgrundlage für Algorithmen zur Bestimmung der Zustandsdichte erarbeitet. Dazu wird ein neues Modellsystem entwickelt, an dem verschiedene Parameter frei gewählt werden können und für das die exakte Zustandsdichte sowie die exakte Übergangsmatrix bekannt sind. Anschließend werden zwei weitere Systeme diskutiert für welche zumindest die exakte Zustandsdichte bekannt ist: das Ising Modell und das Lennard-Jones System. Der dritte Teil der Arbeit beschäftigt sich mit numerischen Untersuchungen an einer Auswahl der vorgestellten Verfahren. Auf Basis der entwickelten Vergleichsgrundlage wird der Einfluss verschiedener Parameter auf die Qualität der berechneten Zustandsdichte quantitativ bestimmt. Es wird gezeigt, dass Übergangsmatrizen in Simulationen mit Wang-Landau-Verfahren eine wesentlich bessere Zustandsdichte liefern als das Verfahren selbst. Anschließend werden die gewonnenen Erkenntnisse genutzt um ein neues Verfahren zu entwickeln mit welchem die Zustandsdichte mittels Minimierung der Abweichungen des detaillierten Gleichgewichts aus großen, dünnbesetzten Übergangsmatrizen gewonnen werden kann. Im Anschluss wird ein Lennard-Jones-System im großkanonischen Ensemble untersucht. Es wird gezeigt, dass durch das neue Verfahren Zustandsdichte und Dampfdruckkurve bestimmt werden können, welche qualitativ mit Referenzdaten übereinstimmen.

La première partie de cette thèse est centrée sur la mission ECLAIRs, dédiée à l'étude de l'émission prompte multi-longueurs d'onde des sursauts γ. Les performances de la caméra X/γ d'imagerie grand champ d'ECLAIRs sont estimées par des simulations Monte-Carlo. La sensibilité de détection des sursauts γ dépend principalement du bruit de fond sur la caméra. En prenant en compte les principales composantes de l'environnement spatial (le fond diffus X extra-galactique, les protons du rayonnement cosmique et atmosphériques, les neutrons atmosphériques, et les photons X-γ de l'albédo terrestre) pour une orbite d'ECLAIRs à 600 km d'altitude et à 20o d'inclinaison, le bruit de fond dans la bande d'imagerie de 4 à 50 keV est estimé à 7,1 coups cm-2 s-1. La sensibilité limite pour un seuil de détection de 5,5 σ de fluctuations du bruit de fond est estimée à 530 milli-Crabe sur une seconde d'intégration dans la bande d'énergie de 4 à 50 keV. Compte tenu des niveaux de bruit de fond, le taux de sursauts γ détectables par an, dans la bande 4-300 keV, est estimé entre 50 et 90 sursauts γ suivant la dureté du sursaut. Pour un échantillon d'une centaine de sursauts détectés, 47% seront localisés à mieux que 10' et 61% à mieux 20' pour un temps d'intégration de 1,024 secondes. Par ailleurs, avec un champ de vue de 105o x 105o et une sensibilité limite de 10 milli-Crabe sur 10 h d'intégration dans la bande 20-200 keV et 3 milli-Crabe dans la bande 4-10 keV, la caméra X-γ fera également un balayage de la sphère céleste, à la recherche de noyaux actifs de galaxies (NAG), de novae X, et de Soft Gamma Repeaters.

Dans la seconde partie de cette thèse, nous nous intéressons à l'apport du code de photo-ionisation, Titan, dans l'interprétation des spectres de haute résolution des NAG, obtenus en X avec les satellites XMM-Newton et Chandra. Nous montrons que les formalismes approchés utilisés pour résoudre le transfert radiatif induisent des interprétations imprécises des spectres des NAG en X, car les flux de raies calculées (notamment les raies de résonance) sont systématiquement surestimés par 30% pour des milieux avec une densité de colonne totale CD < 1021 cm-2 à un ordre de grandeur pour des milieux avec CD > 1024 cm-2. A partir d'une étude théorique du triplet de raies des ions héliumoïdes, nous mettons également en évidence un jeu de diagnostics spectroscopiques. Ces diagnostics permettent de déterminer la densité, la densité de colonne totale et le paramètre d'ionisation des milieux photo-ionisés observés, à partir de la mesure des flux de raies et de la température des continus de recombinaison radiative.

Les propriétés thermodynamiques et mécaniques des fluides confinés à l'échelle sub-microscopique diffèrent profondément de celles du liquide macroscopique. Dans le cadre de la simulation numérique, les études actuelles sur les fluides confinés concernent pour la plupart des cas de haute symétrie où le grand potentiel du système est aisément accessible. Cette limitation restreint grandement le champ des systèmes complexes étudiés théoriquement, alors même que les progrès réalisés dans le domaine des microtechnologies permettent la préparation d'une grande variété de substrats confinants présentant une structure nanométrique. Dans cette thèse nous avons donc développé une méthode de calcul du grand potentiel par intégration thermodynamique applicable aux cas de basse symétrie. Un travail de simulation de Monte Carlo dans l'ensemble Grand Canonique sur un fluide simple confiné dans deux systèmes modèles (où les substrats portent une structure chimique ou géométrique) associé à cette méthode nous a permis de réaliser une étude approfondie du comportement de phase du fluide dans ces systèmes, notamment en identifiant les différentes morphologies que le fluide peut adopter ainsi que leur domaine de stabilité thermodynamique. Nous avons aussi étudié pour la première fois les effets de la torsion sur un fluide confiné. On s'est penché tout particulièrement sur le comportement de phase des morphologies pont (que l'on voit apparaître lors du confinement par des substrats nanostructurés), et sur leur rhéologie lors de la torsion.

L'adsorption de CO dans la faujasite échangée au CuI et au Na+ a été modélisée à l'aide des approches quantiques (DFT) et classiques (Monte Carlo). Grâce à l'approche DFT, la surface d'énergie potentielle de la faujasite a été explorée. Différents types d'interactions de CO avec les cations ont été identifiés, pour chacune les effets induits par l'adsorption de CO aux niveaux structural et énergétique ont été analysés, et le calcul de la fréquence de vibration de CO a été réalisé. Grâce aux valeurs obtenues, une nouvelle attribution des spectres d'adsorption de CO dans CuY et NaY a été établie. D'un autre côté, grâce aux simulations Monte Carlo dans l'ensemble Grand Canonique, les propriétés d'adsorption (isothermes et enthalpies) de la faujasite vis-à-vis de CO ont été modélisées, et le mécanisme microscopique d'adsorption de CO a été établi. La mise en œuvre de ces simulations a nécessité de paramétrer un nouveau champ de force destiné à décrire les interactions CO/faujasite et CO/CO
CO adsorption in CuI and Na+ exchanged faujasite has been modeled by mean of quantum (DFT) and classical (Monte Carlo) approaches. By mean of the DFT calculations, faujasite potential energy surface has been explored. Different types of CO interactions with the cations have been highlighted, for each one of them CO adsorption effects on the structural and energetic parameters have been analyzed, and calculations of the CO stretching frequency have been performed. Thanks to our calculated values, a new attribution of CO adsorption spectra in CuY and NaY has been established. On another side, by mean of Monte Carlo simulations in the Grand Canonical ensemble, faujasite adsorption properties regarding CO (isotherms and enthalpies) have been modeled, and the CO adsorption mechanism has been established at the microscopic level. The implementation of these simulations has required the derivation of a new force field describing the CO/faujasite and CO/CO interactions

Le Modèle Standard, qui décrit les interactions entre les particules à l’échelle quantique, est une théorie imparfaite. Il possède plusieurs problèmes théoriques non-résolus et ne permet pas d’expliquer certaines observations astrophysiques comme celles de la matière noire et de l’asymétrie baryonique. Plusieurs théories, dites au-delà du Modèle Standard, ont été proposées afin de résoudre certains de ces problèmes, et une grande partie d’entre elles prévoient l’apparition de nouveaux phénomènes à haute énergie. L’objectif principal de cette thèse est de rechercher ces phénomènes dans les collisions proton-proton produites par le Large Hadron Collider à une énergie de centre de masse de 13 TeV. Une partie des travaux présentés dans cette thèse a en particulier été dédiée à la recherche de processus de production de quarks top de même signe, c’est-à-dire de même charge électrique, qui sont prédits par des modèles de supersymétrie à R-parité violée. Ces processus engendrent des évènements composés de leptons de même charge accompagnés de b-jets, lesquels ont l’avantage d’être faiblement contaminer par le bruit de fond provenant du Modèle Standard.Les travaux présentés dans cette thèse ont essentiellement porté sur deux analyses, chacune recherchant des phénomènes de nouvelle physique de nature différente dans les évènements composés de leptons de même charge dans les données enregistrées par le détecteur ATLAS. Une première analyse a porté sur la recherche de processus supersymétriques sur les données enregistrées en 2015 et en 2016 avec 36.1 fb$^{-1}$ de luminosité intégrée. Des signaux de production de quarks top de même signe ont été implémentés en se basant sur des processus supersymétriques violant la R-parité, et des régions de signal associées à ces processus ont été optimisées. Une deuxième analyse a porté sur la recherche de processus non-supersymétriques, dits exotiques, dans les données enregistrées en 2015 avec 3.2 fb$^{-1}$ de luminosité intégrée. Cette analyse a surtout été motivée par les résultats obtenus à 8 TeV, dans lesquels un modeste excès de nombre d’évènements par rapport aux prédictions du Modèle Standard a été observé dans deux régions de signal. Une partie des études relatives à cette analyse a été dédiée au développement et à la validation des méthodes d’estimation des différentes sources de bruit de fond.Aucune déviation par rapport aux prédictions du Modèle Standard n’a été observée dans chacune des régions de signal considérées dans les deux analyses. L’excès qui avait été observé dans les résultats obtenus à 8 TeV n’est donc pas confirmé. Des limites d’exclusion sur les modèles de nouvelle physique ont de plus été extraites à partir des résultats obtenus, en particulier sur les modèles de supersymétrie à R-parité violée utilisés pour produire les processus de production de quarks top de même signe
The Standard Model, which describes the particle interactions at quantum level, is an imperfect theory. It has several theoretical problems and is unable to explain astrophysical observations like the dark matter and the baryonic asymmetry of the universe. Several beyond-standard models have been proposed to solve some of these issues, and predict new-physics phenomena at high energy. The aim of this thesis is to search for these phenomena in proton-proton collisions produced by the Large Hadron Collider at a center-of-mass energy of 13 TeV. Part of the studies presented in this thesis was dedicated to the search for production of same-sign top quarks based on R-parity violating supersymmetric models. These processes lead to a signature of same-sign leptons and b-jets, which have the advantage to be lowly contaminated by the Standard Model background.The studies presented in this thesis focused on two analyses, both searching for new-physics phenomena of different nature in same-sign leptons events in data recorded by the ATLAS detector. A first analysis focused on supersymmetric processes with data recorded in 2015 and in 2016 with 36.1 fb$^{-1}$ of integrated luminosity. Same-sign top quarks signals were implemented using R-parity violating supersymmetric processes, and signal regions associated to these processes were optimized. A second analysis focused on exotic (non-supersymmetric) processes with data recorded in 2015 with 3.2 fb$^{-1}$ of integrated luminosity. This analysis was motivated by a modest excess seen in two signal regions in the 8 TeV results. Several studies were focused on the development and the validation of background estimation methods.No deviations from the Standard Model predictions were observed the signal regions considered in both analyses. The 8 TeV excess is therefore not confirmed with the most recent data. Exclusion limits on new-physics models were extracted, in particular for the R-parity violating supersymmetric models that were used to produce the same-sign top quarks processes

Over the last few decades, there has been an increasing interest in the study of charged polymers for applications such as desalination of water, flocculation, sewage treatment, and enhanced oil recovery. Polyelectrolyte chains containing both positively and negatively charged units (polyampholytes) have been recently studied as viscosity-control agents in enhanced oil recovery, and as entrapping macromolecules for protection and delayed release of enzymes in hydraulic fracturing. In this study we performed Monte Carlo molecular simulations in a grand canonical ensemble to study the behavior of a weak polyampholyte in a dilute regime. Weak polyampholytes have the ability to dissociate in a limited pH, which makes them interesting for applications that require a pH-triggerable response. The titration behaviors of diblock and random polyampholytes are simulated as a function of solvent quality, electrostatic strength, and salt concentration. For diblock polyampholyte chains in hydrophobic solvents, transition between tadpole-like and globule conformation occurs with variations in the solution pH. Random polyampholytes present extended, globule, and pearl-necklace conformations at different solvent conditions and pH values. At high ionic strength, electrostatic interactions in the polyampholytes become screened and the chains are mostly in globule state.

This work is divided into two distinct parts. The first part consists of the study of the metal organic framework UiO-66Zr, where the aim was to determine the force field that best describes the adsorption equilibrium properties of two different gases, methane and carbon dioxide. The other part of the work focuses on the study of the single wall carbon nanotube topology for ethane adsorption; the aim was to simplify as much as possible the solid-fluid force field model to increase the computational efficiency of the Monte Carlo simulations. The choice of both adsorbents relies on their potential use in adsorption processes, such as the capture and storage of carbon dioxide, natural gas storage, separation of components of biogas, and olefin/paraffin separations. The adsorption studies on the two porous materials were performed by molecular simulation using the grand canonical Monte Carlo (μ,V,T) method, over the temperature range of 298-343 K and pressure range 0.06-70 bar. The calibration curves of pressure and density as a function of chemical potential and temperature for the three adsorbates under study, were obtained Monte Carlo simulation in the canonical ensemble (N,V,T); polynomial fit and interpolation of the obtained data allowed to determine the pressure and gas density at any chemical potential. The adsorption equilibria of methane and carbon dioxide in UiO-66Zr were simulated and compared with the experimental data obtained by Jasmina H. Cavka et al. The results show that the best force field for both gases is a chargeless united-atom force field based on the TraPPE model. Using this validated force field it was possible to estimate the isosteric heats of adsorption and the Henry constants. In the Grand-Canonical Monte Carlo simulations of carbon nanotubes, we conclude that the fastest type of run is obtained with a force field that approximates the nanotube as a smooth cylinder; this approximation gives execution times that are 1.6 times faster than the typical atomistic runs.

Graphene oxide (GO) is a chemically functionalized graphene with various oxygen-containing functional groups, such as epoxy (-O-), hydroxyl (-OH), and carboxyl (-COOH) on the basal plane. As a consequence, GOs have hydrophilic and hydrophobic regions at the molecular level. GO membranes are found to be a promising potential material for water filtration and desalination, gas separations, and fuel cell applications. The GO structure is non-unique and complex in nature due to variations in the extent of the oxidized regions. In this thesis, we use molecular simulations to understand the structure and dynamics of water confined in GO nanopores and on GO surfaces, as well as the manner in which the extent of hydrophobicity modulates these properties. In the first part of this thesis, we model the GO surface to represent various scenarios. Here we study the adsorption of water on a GO surface as a function of varying levels of hydrophobicity using grand canonical Monte Carlo (GCMC) simulations. GCMC simulations reveal interesting water film growth as the vapor pressure is increased. Water is found to adsorb at the hydrophilic - hydrophobic interface at low pressures. Subsequently, a water bridge spanning the hydrophilic region is observed, and large number fluctuations are observed due to the Janus nature of the interface. The extent of hydrophobicity determines water layering, organization, and the adsorption isotherms. We investigate the influence of surface chemistry on the dynamical transitions of supercooled interfacial water on the GO surface. Using the TIP4P/2005 water model, molecular dynamics (MD) simulations reveal that the rotational relaxation of bound water can undergo either a strong-to-strong or a single Arrhenius behaviour as a function of the surface hydrophilicity. This is in contrast to bulk water, which exhibits a fragile-to-strong transition upon supercooling. Molecular dynamics simulations on surface water where the influence of bulk-like water is absent, revealed a single Arrhenius behaviour during supercooling. Our results provide novel insights into the strong role played by the presence of bulk water as well as the influence of surface chemistry on the dynamical transitions of interfacial water. In order to understand the influence of surface oxidation and the inherent heterogeneity imposed by opposing surfaces formed in macroscopic membranes, MD simulations of water confined in nanopores (8 - 15 Angstrom) made up of different surface types are carried out . The greatest differences are observed at 8 Angstrom, which is the optimal separation distance for molecular sieving of ions. The dipole-dipole relaxation and HH rotational relaxation of confined water are the slowest between fully oxidized (OO) surfaces with a two-order decrease in the dipole-dipole relaxation time observed for the Janus confinement consisting of an oxidized surface adjacent to a graphene surface. Although the water diffusivity is an order of magnitude smaller than bulk diffusivities at the smaller surface separations, water between the Janus surfaces always had the highest diffusivities. Thus the Janus interface appears to provide the optimal environment for water transport, providing a design strategy while assembling GO-based membrane for water purification. Molecular dynamics simulations have been carried out to explore the dynamical crossover phenomenon in strongly confined and layered water in GO nanopores. In contrast to studies where confinement is used to study the properties of bulk water, we are interested in the dynamical transitions for strongly confined water in the absence of any bulk-like water. Graphene oxide surfaces having different degrees of hydrophilicity are placed at interlayer separation of d = 10 Angstrom, to produce an in-registry pore (IR) and a fully hydrophilic (OO) nanopore. Water confined in the IR pores exhibits a strong-to-strong dynamical transition in the diffusion coefficient and rotational relaxation time at 237 K and shows a fragile-to-strong transition in the alpha-relaxation at 238 K. In contrast, water confined in the OO pores did not display a dynamical crossover in any of the dynamical quantities studied. Our results indicate that water under strong confinement can undergo a dynamic transition, which is a strong function of the physicochemical nature of the confining surface. In the last part of this thesis, we have studied the adsorption of pure CH4, CO2, N2, and H2 gases in GO nanopores of d = 10 Angstrom using grand canonical Monte Carlo (GCMC) simulations and have also evaluated adsorption selectivity for equimolar gas mixtures of CH4/CO2, CO2/N2, CO2/H2, and CH4/H2 in GO nanopores of d = 10 Angstrom at 298 K. Adsorption isotherm and isosteric heats of adsorption reveal that CO2 adsorption is highest, and adsorption of H2 is lowest. Adsorption selectivity of CO2 in all gas mixtures for the GO pores is highest, specifically in the CO2/H2 mixture, and in the case of the CH4/H2 mixture, CH4 selectivity is higher. These findings suggest that GO nanopores have the potential to be used as adsorbents for the CO2 capture from flue gas and natural gas streams.

Thesis (Ph. D.)--University of Wisconsin--Madison, 1991.
Typescript. Vita. eContent provider-neutral record in process. Description based on print version record. Includes bibliographical references.

Thesis (M.S.)--State University of New York at Buffalo, 2007.
Title from PDF title page (viewed on unex. 17, 2008) Available through UMI ProQuest Digital Dissertations. Thesis adviser: Errington, Jeffrey R., Kofke, David A. Includes bibliographical references.

We introduce an efficient thermodynamically consistent technique to extrapolate and interpolate normalized Canonical NVT ensemble averages like pressure and energy for Lennard-Jones (L-J) fluids. Preliminary results show promising applicability in oil and gas modeling, where accurate determination of thermodynamic properties in reservoirs is challenging. The thermodynamic interpolation and thermodynamic extrapolation schemes predict ensemble averages at different thermodynamic conditions from expensively simulated data points. The methods reweight and reconstruct previously generated database values of Markov chains at neighboring temperature and density conditions. To investigate the efficiency of these methods, two databases corresponding to different combinations of normalized density and temperature are generated. One contains 175 Markov chains with 10,000,000 MC cycles each and the other contains 3000 Markov chains with 61,000,000 MC cycles each. For such massive database creation, two algorithms to parallelize the computations have been investigated. The accuracy of the thermodynamic extrapolation scheme is investigated with respect to classical interpolation and extrapolation. Finally, thermodynamic interpolation benefiting from four neighboring Markov chains points is implemented and compared with previous schemes. The thermodynamic interpolation scheme using knowledge from the four neighboring points proves to be more accurate than the thermodynamic extrapolation from the closest point only, while both thermodynamic extrapolation and thermodynamic interpolation are more accurate than the classical interpolation and extrapolation. The investigated extrapolation scheme has great potential in oil and gas reservoir modeling.That is, such a scheme has the potential to speed up the MCMC thermodynamic computation to be comparable with conventional Equation of State approaches in efficiency. In particular, this makes it applicable to large-scale optimization of L-J model parameters for hydrocarbons and other important reservoir species. The efficiency of the thermodynamic dependent techniques is expected to make the Markov chains simulation an attractive alternative in compositional multiphase flow simulation.