A number of novel hydrocarbon cage systems have been designed and characterized using ab initio molecular orbital calculations at the MP2 and B3-LYP levels. In particular,equilibrium structures for five families of molecules, hemialkaplanes, hemispiroalkaplanes, alkaplanes, spiroalkaplanes and dimethanospiroalkaplanes, have been examined in detail with the aim of designing a saturated hydrocarbon with a planar-tetracoordinate carbon atom and with a view to identifying appropriate synthetic targets. ¶ The hemialkaplanes and hemispiroalkaplanes are constructed from a spiropentane or neopentane subunit, respectively, which is capped by a cyclic hydrocarbon. The hemispiroalkaplanes are predicted to contain a pyramidal-tetracoordinate carbon atom possessing a lone pair of electrons. Protonation at this apical carbon atom is found to be highly favorable, resulting in a remarkably high basicity for a saturated hydrocarbon. The proton affinities of the hemispiroalkaplanes are calculated to be more than 1170 kJ mol[superscript -1] , even greater than those for the diamine "proton sponges". ¶ The alkaplanes and the spiroalkaplanes, which are constructed by bicapping a neopentane or spiropentane subunit, respectively, with a pair of cyclic hydrocarbons, show unprecedented flattening of a tetracoordinate carbon atom. Linking the spiroalkaplane caps with methano bridges gives the dimethanospiroalkaplanes, two of which, dimethanospirooctaplane and dimethanospirobinonaplane, achieve exact planarity at the central carbon atom. They are the first neutral saturated hydrocarbons predicted to contain an exactly planartetracoordinate carbon atom. This has been achieved through structural constraints alone. The electronic structure at the central carbon atom results in a highest occupied molecular orbital corresponding to a p-type lone pair. Consequently, the adiabatic ionization energies for octaplane, spirooctaplane and dimethanospirooctaplane (approximately 5 eV) are predicted to be similar to those of lithium and sodium - incredibly low for a saturated hydrocarbon. ¶ Some consideration has been given to likely pathways for unimolecular decomposition for all species. Predicted structures, heats of formation and strain energies for all the novel hydrocarbons are also detailed. Tetramethylhemispirooctaplane and dimethanospirobinonaplane are identified as the preferred synthetic targets.

The CANDU Supercritical Water-Cooled Reactor’s extreme operating conditions and single-loop design have fuelled a need for better understanding of hydrothermal chemistry. This thesis reports the thermal stability and decomposition kinetics of perchloric acid in quartz and Pyrex® cells. HClO4 is an appropriate internal standard for Raman measurements of nickel(II) chloro complexes in quartz cells up to 200 ºC Raman spectroscopy. This thesis also reports the first Raman spectra for Ni2+, NiCl+ and NiCl2 from 8 to 120 ºC. Due to very weak bands and overlap of the contributing species, a thermodynamic speciation model, principle component analysis, and quantum mechanical predictions of the nickel(II) chloro Raman spectra were required to assign peaks. The assignment was confirmed by calculating temperature independent scattering coefficients from the spectra. This is the first study to obtain a spectrum for NiCl2 below 100 ºC. / University of Guelph, Atomic Energy of Canada Limited (AECL), Bruce Power, University Network of Excellence in Nuclear Engineering (UNENE), National Sciences and Engineering Research Council of Canada (NSERC), Natural Resources Canada, Ontario Power Generation (OPG), Canada Foundation for Innovation

La demande d'une énergie durable et verte est très importante pour les gouvernements et les populations. De par l'augmentation rapide de la population humaine et l'industrialisation à l'échelle mondiale, c’est devenu un enjeu majeur. Une alternative à l’utilisation des combustibles fossiles qui peut être envisagée est l’utilisation, lorsque c’est possible, de dispositifs thermoélectriques. Ces derniers peuvent convertir la chaleur perdue, provenant de diverses sources, en énergie électrique. Cependant, les dispositifs thermoélectriques actuels sont limités en raison de leur faible efficacité, de la nature toxique des matériaux utilisés et de leurs coûts élevés. Le défi actuel dans ce domaine de recherche est de concevoir des matériaux hautement efficaces, respectueux de l'environnement et disponibles à des prix moins élevés. Parmi les matériaux thermoélectriques prometteurs pour la génération d'énergie, le composé Fe2VAl (matériau de la famille des composés Heusler), semble prometteur car il se comporte comme un semi-conducteur sur une large gamme de température et ce jusqu'à 1173 K. Néanmoins, la capacité thermoélectrique de ce composé est compromise par sa conductivité thermique élevée. L'objectif de cette thèse était de trouver de nouvelles stratégies afin d’améliorer l'efficacité thermoélectrique de Fe2VAll'aide de calculs ab initio et d'études expérimentales. Les calculs basés sur les premiers principes ont été effectués en utilisant le code informatique VASP (Vienna Ab-initio Simulation Package) basé sur la théorie de la fonctionnelle densité (DFT) avec comme but d’étudier la structure électronique du composé Fe2VAl. L'énergie de formation des défauts intrinsèques tels que les lacunes, les anti-sites et les défauts interstitiels, a été déterminée. Nous avons montré que la formation des défauts de type anti-sites est la plus probable. À l'aide du code BoltzTraP, basé sur la théorie du transport de Boltzmann dans l’approximation du temps de relaxation constant, les propriétés de transport électronique de Fe2VAl pur et contenant les défauts les plus favorables ont été calculées. La présence des différents défauts au sein du réseau n’entraine pas d'amélioration notable du coefficient de Seebeck. La conductivité thermique de réseau de Fe2VAl, à la fois sous forme pure et en présence des défauts d’anti-site les plus stables (AlV) a été analysée en utilisant les codes ShengBTE et almaBTE récemment développés. Uneamélioration significative du facteur de mérite (appelé ZT) est alors trouvée en présence de défauts de type anti-sites. Des composés Fe2VAl nanostructurés ont été synthétisés en parallèle par mécanosynthèse, autrement appelé broyage hauteénergie. Les éléments constitutifs sont broyés en ajoutant différentes proportions de chlorure de sodium afin d'obtenir des échantillons poreux, NaCl servant d’agent structurant. Les poudres sont ensuite lavées soigneusement pour éliminer les traces de NaCl et consolidées à l'aide de la technique de frittage flash SPS. L’utilisation de cette nouvelle voie pour structurer et introduire de la porosité dans les échantillons afin de diminuer la conductivité thermique est assez concluante. Nous obtenons une porosité d'environ 15 à 20% en présence de NaCl (contre environ 5% sans sel). L'efficacité thermoélectrique estremarquablement augmentée pour ces échantillons poreux. Néanmoins, les échantillons broyés contenant 15% de porosité présentent des valeurs de ZT plus élevées que les échantillons à plus forte porosité. Ainsi, il est crucial de contrôler et d’optimiser la porosité pour obtenir une plus grande efficacité thermoélectrique. Notre étude montre ainsi clairement que la performance thermoélectrique peut être améliorée en modifiant la stœchiométrie et la morphologie des échantillons.Mots clés : Fe2VAl, matériaux, composés Heusler, thermoélectricité, calculs ab initio, enthalpie de formation, défauts, mécanosynthèse, porosité. / The requirement of a sustainable and green energy is increasing with the rapid rise in human population and industrialization. The traditional way of utilizing fossil fuels can be replaced by thermoelectric devices which can convert thewasted heat from various sources into electrical energy. However, the present day thermoelectric devices are limited due to their low efficiency, toxic nature and high costs. The current challenge in this field is to design highly efficient thermoelectric materials which are environment friendly and available at a reasonable price. Among promising thermoelectric materials forpower generation, the Heusler-type Fe2VAl attained a great attention due to its semiconducting nature over a wide temperature range up to 1173 K. Nonetheless, the thermoelectric use of this compound is jeopardized by its high thermalconductivity. The aim of this thesis was to find new strategies in enhancing the thermoelectric efficiency of Fe2VAl with the aid of ab initio calculations and experimental studies. First principles calculations have been performed using the computer code VASP (Vienna ab-initio Simulation Package) based on the Density Functional Theory (DFT) to study the electronic structure of the full Heusler compound Fe2VAl. The formation energy of the intrinsic point defects such as vacancies, antisites and interstitials is analyzed and antisite defects are found to be the most probable defects. With the aid of the BoltzTraP code based on the Boltzmann transport theory within the constant relaxation time approach, the electronic transport properties of Fe2VAl taking into account the effect of the most favorable defects have been calculated. The presenceof defects does not lead to a significant improvement of the Seebeck coefficient. The lattice thermal conductivities of Fe2VAl, both in pristine form and in presence of its most stable antisite defect (Al V) have been analyzed by ShengBTE and the recently developed code almaBTE. A significant enhancement of the figure of merit (also known as ZT) is found with the presence of antisite defects. Nanostructured Fe2VAl compounds have been synthesized in parallel by the ball milling technique. The constituent elements have been milled together with different contents of NaCl in order to obtain porous samples. The powders have been later washed thoroughly to remove the traces of NaCl. All the powders have been consolidated using Spark Plasma Sintering (SPS). This novel idea is quite successful in achieving a porosity of around 15–20% with NaCl whereas a porosity of ~5 % is found in the case of the samples without NaCl. The thermoelectric efficiency is enhanced remarkably in the porous samples. Nevertheless, the samples milled with 15 % porosity exhibit higher ZT valuesthan the samples with 20 % porosity. Thus, it is crucial to confine and control the porosity to obtain high thermoelectric efficiencies. Our study thus clearly shows that the thermoelectric performance can be enhanced by off-stoichiometry and the modification of the morphology of the samples.Key words: Fe2VAl, materials, Heusler compounds, thermoelectricity, ab initio calculations, formation enthalpy, defects, ball milling,porosity.

This master's thesis studies the electronic properties changes of graphene caused by substrate SiO2, adsorbed molecules of water and atoms of gallium. There are tested different geometrical configurations of these systems and consequently calculated band structures to derive the changes of the electronic properties: the doping effect and band gap opening of graphene layer.

<div>The recent decades have witnessed increased efforts to push the efficiency of energy systems beyond existing limits in order to keep pace with the rising global energy demands. Such efforts involve finding bulk materials and nanostructures with desired thermal properties such as thermal conductivity (k). For example, identifying high k materials is crucial in thermal management of vertically integrated circuits (ICs) and flexible nanoelectronics, which will power the next generation personal computing devices. On the opposite end of the spectrum, designing ultra-low k materials is essential for improving thermal barrier coatings in turbines and creating high performance thermoelectric (TE) devices for waste heat harvesting. In this dissertation, we identify nanostructures with such extreme thermal transport properties and explore the underlying phonon and photon transport mechanisms. Our approach follows two main avenues for evaluating potential candidates: (a) high fidelity atomistic simulations and (b) rapid machine learning-based property prediction and design optimization. The insight gained into the governing physics enables us to theoretically predict new materials for specific applications requiring high or low k, propose accelerated design optimization pathways which can significantly reduce design time, and advance the general understanding of energy transport in semiconductors and dielectric materials.</div><div><br></div><div>Bi2Te3, Sb2Te3 and nanostructures have long been the best TE materials due to their low κ at room temperatures. Despite this, computational studies such as molecular dynamics (MD) simulations on these important systems have been few, due to the lack of a suitable interatomic potential for Sb2Te3. We first develop interatomic potential parameters to predict thermal transport properties of bulk Sb2Te3. The parameters are fitted to a potential energy surface comprised of density functional theory (DFT) calculated lattice energies, and validated by comparing against experimental and DFT calculated lattice constants and phonon properties. We use the developed parameters in equilibrium MD simulations to calculate the thermal conductivity of bulk Sb2Te3 at different temperatures. A spectral analysis of the phonon transport is also performed, which reveals that 80% of the total cross-plane k is contributed by phonons with mean free paths (MFPs) between 3-100 nm. </div><div><br></div><div>We then use MD simulations to calculate phonon transport properties such as thermal conductance across Bi2Te3 and Sb2Te3 interface, which may account for the major part of the total thermal resistance in nanostructures. By comparing our MD results to an elastic scattering model, we find that inelastic phonon-phonon scattering processes at higher temperatures increases interfacial conductance by providing additional channels for energy transport. Finally, we calculate the thermal conductivities of Bi2Te3/Sb2Te3 superlattices (SLs) of varying period. The results show the characteristic minimum thermal conductivity, which is attributed to the competition between incoherent and coherent phonon transport regimes. Our MD simulations are the first fully predictive studies on this important TE system and pave the way for further exploration of nanostructures such as SLs with interface diffusion and random multilayers (RMLs).</div><div><br></div><div>The MD simulations described in the previous section provide high-fidelity data at a high computational cost. As such, manual intuition-based search methods using these simulations are not feasible for searching for low-probability-of-occurrence systems with extreme thermal conductivity. In view of this, we use machine learning (ML) techniques to accelerate and efficiently perform nanostructure design optimization within such large design spaces. First, we use a Genetic Algorithm (GA) based optimization method to efficiently search the design space of fixed length Si/Ge random multilayers (RMLs) for the structure with lowest k, which is found to be lower than the SL k by 33%. By comparing thermal conductivity and interface resistances between optimal and sub-optimal structures, we identify non-intuitive trends in design parameters such as average period and degree of randomness of layer thicknesses. </div><div><br></div><div>While machine learning (ML) has shown increasing effectiveness in optimizing materials properties under known physics, its application in discovering new physics remains challenging due to its interpolative nature. We demonstrate a general-purpose adaptive ML-accelerated search process that can discover unexpected lattice thermal conductivity (k) enhancement in aperiodic superlattices (SLs) as compared to periodic superlattices, with implications for thermal management of multilayer-based electronic devices. We use molecular dynamics simulations for high-fidelity calculations of k, along with a convolutional neural network (CNN) which can rapidly predict k for a large number of structures. To ensure accurate prediction for the target unknown SLs, we iteratively identify aperiodic SLs with structural features leading to locally enhanced thermal transport and include them as additional training data for the CNN. The identified structures exhibit increased coherent phonon transport owing to the presence of closely spaced interfaces.</div><div><br></div><div>We also demonstrate the application of ML in optimization of photonic multilayered structures with enhanced reflectivity to radiation heat flux, which is required for applications such as high temperature thermal barrier coatings (TBCs). We first perform a systematic variation of design parameters such as total thickness and average layer thickness of CeO2-MgO multilayers, and quantify their influence on the spectral and total reflectivity. The effect of randomization of layer thicknesses is also studied, which is found to increase the reflectivity due to localization of photons in certain spatial regions of the multilayer structure. Next, we employ a GA search method which can efficiently identify RML structures with reflectivity enhancements of ~22%, 20%, 20% and 10% over that obtained in randomly generated RML structures for total thicknesses of 5,10,20 and 30 microns respectively. We also calculate the spectral reflectivity and the field intensity distribution within the optimal and sub-optimal RML structures. We find that the electric field intensity can be significantly enhanced within certain spatial regions within the GA-optimized RMLs in comparison to non-optimized and periodic structures, which implies the high degree of randomness-induced photon localization leading to enhanced reflectivity in the GA-optimized structures.</div><div><br></div><div>In summary, our work advances the design or search for materials and nanostructures with targeted thermal transport properties such as low and high thermal conductivity and high reflectivity. The new insights provided into the underlying physics will guide the design of promising nanostructures for high efficiency energy systems. </div><div><br></div>

In order to study the electronic and optical properties of complex materials an approach providing a reliable estimate of band gaps in combination with the reasonable description of the ground state is required. In the present study of pure and defective perovskite crystals, the fulfillment of such requirements is clearly demonstrated using a simple hybrid HF/DFT scheme containing an admixture of non-local Fock exchange. In present theoretical investigations, a wide class of perovskite oxides is represented by three, the most attractive (from a scientific point of view) crystals of SrTiO3, BaTiO3, and PbTiO3 in their high symmetry cubic phases. These perovskite crystals present a great technological and fundamental interest due to their numerous applications related to ferroelectricity, non-linear and electro-optics, superconductivity, and catalysis. Although the above-mentioned perovskite-type materials have been intensively investigated theoretically and experimentally at least in the last fifteen years, a proper description of their electronic properties is still an area of active research. In order to make a contribution to the explanation of various electro-optical effects observed in perovskite materials, their ground-state properties have been calculated from first principles and analyzed in the present study.

The importance of radical-water complexes in the atmosphere is explored in this dissertation. Radicals, although present in small concentrations in the atmosphere, play a significant role in creating and removing atmospheric pollution. As the atmosphere warms and consequently gets wetter, it is essential to understand the effects of water vapor on radical chemistry. This dissertation reports studies on the effects of water vapor on the kinetics of the self-reaction of β-hydroxyethyl peroxy radical (β-HEP), a prominent organic peroxy radical in the atmosphere. Both experimental and computational studies have been performed to examine the effects of water vapor on the kinetics of the self-reaction. The influence of water vapor and temperature on the reaction rate constant is presented. The rate of the self-reaction increases between 2 to 6 times with an increase in water vapor and decrease in temperature. The products of the self-reaction in the presence and absence of water vapor have been computed using high level ab initio calculations. Major products include alkoxy radicals, peroxides, aldehydes, alcohols and oxygen. A new reaction pathway leading to formation of hydroperoxy radical (HO2) from the self-reaction of β-HEP in the presence of water vapor was identified. In the presence of high NOx concentration HO2, forms tropospheric ozone, which is classified as a harmful pollutant by the Environmental Protection Agency (EPA). Like tropospheric ozone, aerosols are also classified as harmful pollutants by the EPA. Sulfuric acid-water complexes are estimated to be the primary reason for new aerosol formation in the atmosphere. However, the sulfuric acid concentration in the atmosphere alone is not sufficient to account for observed aerosol concentrations. Classical nucleation theory is used to explain new particle formation (NPF), which is initiated by the formation of a nucleating site (a highly polar complex). This dissertation explores the role of various radical-molecule complexes acting as the nucleating site. Experimentally, the HO2-water complex is studied as a possible nucleating site for NPF. A new instrument was developed to create and measure radical-water complex initiated particle formation. The instrument incorporates two scanning mobility particle sizers (SMPS) to measure the size distribution and number density of the aerosol particles formed. The experimental setup uses UV absorption spectroscopy and wavelength modulated spectroscopy to measurethe HO2 radical and water vapor concentrations in the reaction cell. No significant particle formation was observed at room temperature and pressure. Particle formation from the HO2-water complex, may occur at lower temperatures. Additional radical-molecule complexes have been studied computationally in an effort to identify other possible nucleating sites for particle formation. In particular, the complexes of sulfuric acid, nitric acid, acetic acid and formic acid with ammonia, amidogen radical (NH2) and imidogen radical (NH) have been studied. H2SO4-NH2 and HNO3-NH2 complexes show the potential to act as nucleating sites for formation of aerosol particles in the atmosphere. In summary, water mediated chemistry plays a significant role in the atmosphere and must be included in scientific models to better predict pollution levels in the atmosphere.

This dissertation is a collection of works that investigate non-prototypical sources leading to new particle formation in the atmosphere. Particles play a major role in atmospheric chemistry. For example, particles are a component of smog and are commonly found in high concentrations under conditions of atmospheric inversions. In order to reconcile the difference between measured and modeled particle concentrations new mechanisms from non-prototypical sources for particle formation need to be determined. Formation of particles has frequently been modeled using classical nucleation theory (CNT). The first step in CNT is the nucleation step where molecular clusters form. In a second step, these clusters grow into particles through coagulation or condensation. First, this research aims to improve the modeling of equilibrium constants for the formation of peroxy radical-water complexes. Failure of the harmonic approximation in the partition function for describing the low frequency vibrational modes of the complexes was explored. Instead the dissociative hydrogen bond mode using a Lennard-Jones 6-3 potential and the other low frequency vibrational modes using one- and two-fold hindered rotors was modeled. It was determined that the contribution of the two-fold hindered rotors is more important than the long-range dipole-dipole potentials and of vibration-rotation coupling. In related work, the hydroperoxy radical was investigated as a non-prototypical source of particles using high level ab initio calculations. The results indicate that the addition of an amine to the dimer increased the overall stability of complex through the increased number and strength of the hydrogen bonds. When compared to prototypical systems, sulfuric acid and methane sulfonic acid, the strength of the complex was found to be similar to the peroxy radical system. Finally, carboxylic acids, formic acid and acetic acid, were investigated as a source for new particle formation using computational and experimental techniques. Using a slow flow reactor cell particle formation was enhanced by the addition of trimethylamine. High level ab initio calculations indicate like the peroxy radicals, carboxylic acids may act as a molecular cluster in particle formation

Heteroanionic hydrides offer great possibilities in the design of functional materials. For ternary rare earth hydride oxide REHO, several modifications were reported with indications for a significant phase width with respect to H and O of the cubic representatives. We obtained DyHO and ErHO as well as the thus far elusive LuHO from solid-state reactions of RE2O3 and REH3 or LuH3 with CaO and investigated their crystal structures by neutron and X-ray powder diffraction. While DyHO, ErHO, and LuHO adopted the cubic anion-ordered half-Heusler LiAlSi structure type (F4¯3m, a(DyHO) = 5.30945(10) Å, a(ErHO) = 5.24615(7) Å, a(LuHO) = 5.171591(13) Å), LuHO additionally formed the orthorhombic anti-LiMgN structure type (Pnma; LuHO: a = 7.3493(7) Å, b = 3.6747(4) Å, c = 5.1985(3) Å; LuDO: a = 7.3116(16) Å, b = 3.6492(8) Å, c = 5.2021(7) Å). A comparison of the cubic compounds’ lattice parameters enabled a significant distinction between REHO and REH1+2xO1−x (x < 0 or x > 0). Furthermore, a computational chemistry study revealed the formation of REHO compounds of the smallest rare earth elements to be disfavored in comparison to the sesquioxides, which is why they may only be obtained by mild synthesis conditions.

<p>In the present work, the structural, electronic properties, thermodynamic stability and adatom surface movements of oxygen and sulfur adsorption on the Fe surface were studied based on the ab initio method.</p><p>Firstly, the oxygen adsorbed on the iron (100) surface is investigated at the three adsorption sites top, bridge and hollow sites, respectively. Adsorption energy, work function and surface geometries were calculated, the hollow site was found to be the most stable adsorption site, Which is in agreement with the experiments. In addition, the difference charge density of the different adsorption systems was calculated to analyze the interaction and bonding properties between Fe and O. It can be found out that the charge redistribution was related to the geometry relaxation.</p><p>Secondly, the sulfur coverage is considered from a quarter of one monolayer (1ML) to a full monolayer. Our calculated results indicate that the most likely site for S adsorption is the hollow site on Fe (100). We find that the work function and its change Df increased with S coverage, in very good agreement with experiments. Due to a recent discussion regarding the influence of charge transfer on Df, we show that the increase in Df can be explained by the increasing surface dipole moment as a function of S coverage. In addition, the Fe-S bonding was analyzed. Finally, the thermodynamic stabilities of the different structures were evaluated as a function the sulfur chemical potential.</p><p>Finally, a two dimensional (2D) gas model was proposed to simulate the surface active elements, oxygen and sulfur atoms, movement on the Fe (100) surface. The average velocity of oxygen and sulfur atoms was found out to be related to the vibration frequencies and energy barrier in the final expression developed. The calculated results were based on the density function and thermodynamics & statistical physics theories. In addition, this 2D gas model can be used to simulate and give an atomic view of the complex interfacial phenomena in the steelmaking refining process.</p>