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Ring closing metathesis (RCM) is a chemical transformation that converts a bisalkene compound into a cycloalkene. It is catalyzed by transition metal complexes containing carbene ligands (that feature metal-carbon double bonds). The mechanism is well-understood, however, there are numerous details of the reaction that are less well understood, especially concerning catalyst activation and decomposition and formation of byproducts. This thesis takes a new approach to the study of RCM: analysis of the reaction using real-time mass spectrometric techniques. Electrospray ionization (ESI) mass spectrometry was employed in this study, and the real-time aspect was enabled by using pressurized sample infusion (PSI). Observation of the reactants and products was enabled using charge-tagged bis-alkenes of the general formula [Bu2N{(CH2)nCH=CH2}2]+ [PF6]–. These were synthesized in two steps using a generally applicable methodology to generate a wide range of ring sizes of the product, from 5- to 15-membered rings. Examination of their behavior under carefully optimized RCM conditions using Grubbs’ second-generation catalyst showed a wide variation in reaction rates and amount of byproducts, largely due to ring-strain effects (especially high for 5- and 9-membered rings). Byproducts always exhibited a 14 Da mass unit difference from starting materials or products, and Orbitrap MS analysis confirmed it was CH2. Isomerization was suspected to lead to byproducts. A pathway for byproducts via isomerization and cross metathesis was proposed. The source of actual isomerization catalyst was believed to be from the precatalyst itself as the evidence of precatalyst decomposition was observed. Finally, to prove our isomerization hypothesis, an authentic isomerization catalyst was deliberately added into a fast and clean reaction along with Grubbs’ second-generation catalyst, and it produced the expected byproducts. Only small amounts of oligomeric intermediates were observed, probably because of the low concentrations used. [ClPCy3]+ was a new short-lived decomposition product stemming from catalyst breakdown, along with already-known imidazolium and protonated phosphine decomposition products. Overall, the thesis provides deep new insights into the nature of RCM reactions, in particular revealing the importance of isomerization in RCM reactions that are slow due to ring strain effects and in uncovering a new decomposition pathway for important RCM catalysts. / Graduate

This thesis describes searches for a heavy charged Higgs boson decaying into a top and bottom quark pair, and the development of a hardware track trigger with theATLAS experiment. The data for the two searches was collected with the ATLAS detector at the Large Hadron Collider(LHC) with pp collision energies of √s = 8 and 13 TeV, and corresponds to an integrated luminosity of 20.3 and 13.2 fb-1 respectively. The main background for this signal is the production of tt̄ pairs with additional heavy flavor radiation. The searches with a single lepton in the final state found no evidence of a charged Higgs boson, and set 95% CLS upper limits on the production times branching ratio for masses ranging between 200-1000 GeV. The preparation of using the final state with two leptons in future searches is discussed. The design of a hardware track trigger based on pattern matching and linear track fitting was studied for the purpose of reducing the high event rates of the High-Luminosity LHC, which is expected to provide pp collisions with a luminosity about five times the nominal value, in the second half of the 2020’s. A simulation framework was developed to emulate the pattern matching and was used to test its ability to filter hits in high pile-up environments. The results of this simulation, together with simulations of the track fitting and latency, show that such a track trigger is a viable option for the ATLAS experiment in the High Luminosity-LHC era.

L'étude des plasmas poussiéreux est maintenant un domaine scientifique en plein développement qui attire l'attention d’une large communauté de scientifiques. Rappelons que le plasma poussiéreux est un plasma classique avec des particules injectées ou qui s’y sont formées dont les tailles peuvent atteindre quelques micromètres. Ces particules (poussières) peuvent acquérir de très grandes charges jusqu'à 103 à 105 charges élémentaires. Dans la littérature, il est également appelé plasma à phase condensée dispersée, plasma aérosol et aussi plasma complexe. Les plasmas poussiéreux sont d’un grand intérêt à la fois sur le plan pratique afin de trouver des solutions à des problèmes industriels et sur le plan scientifique fondamental afin d’élargir nos connaissances sur les phénomènes fondamentaux de la nature ainsi que les propriétés et la structure de la matière. En raison du fait que les particules de poussière macroscopique sont visuellement distinguables, le plasma poussiéreux est un objet d’étude unique pour l'étude de certaines propriétés physiques de la matière condensée, telles que les transitions de phase, la propagation d’ondes, les phénomènes de dislocation, les processus de transport, etc…On a constaté que dans de nombreuses technologies modernes mettant en oeuvre un plasma, en raison de l'interaction du plasma avec la surface des matériaux, des particules macroscopiques sont éjectées de celles-ci dans le plasma (dont les tailles peuvent être de quelques nanomètres jusqu'à quelques dizaines de micromètres). Il en résulte ainsi la formation d’un plasma complexe. Le nom le plus commun de ce plasma est un plasma poussiéreux. Un des aspects les plus intéressants est la formation dans certaines conditions de structures ordonnées (« cristaux ou liquide coulombiens »). Toutes ces structures plasmapoussière, se formant de façon naturelle, sont une contamination indésirable qui affecte négativement les propriétés physiques et mécaniques (micro dureté, résistance à la corrosion, etc.) des matériaux et dispositifs manufacturés.L'un des problèmes scientifiques et technologiques les plus importants, à l’heure actuelle, est la réalisation de la fusion thermonucléaire contrôlée. Dans ces conditions extrêmes se forment aussi au voisinage des parois des Tokamaks des poussières qui jouent un rôle fondamental : les données expérimentales récentes montrent que la présence de poussières dans le plasma peut affecter le temps global de confinement du plasma. L'utilisation du plasma poussiéreux dans la production de matériaux composites, à haute valeur ajoutée, est un nouveau champ d'applications. On peut citer à titre d’exemples, le traitement de surface de petites particules sphériques avec des revêtements, d’épaisseur nanométrique, déposés par plasma. Afin d'étudier les mécanismes de formation de particules homogènes ayant des propriétés désirées et une production stable, il est nécessaire de trouver les conditions optimales de production. Ainsi, l'étude des propriétés des plasmas poussiéreux et leurs diagnostics sont des tâches très importantes, à la fois pour les connaissances scientifiques fondamentales et que pour les aspects appliqués. / The study of the dusty plasma is now a developing scientific field, attracting the attention of scientists. Recall that the dusty plasma is conventional plasma with inserted or formed therein particles of condensed matter of microns sizes, the size of these particulates (dusts) can acquire very large charges up to 3 5 10 ¸10 of the elementary charges. In the literature, it is also named as plasma with a condensed dispersed phase, aerosol plasma. Dusty plasma is of interest both for the solution of the applied problems, and to expand our knowledge of the fundamental phenomena in nature, properties and structure of matter. Due to the fact that the macroscopic dust are visually distinguishable the dispersed plasma is unique comfort object for the study of some physical properties of condensed matter, such as phase transitions, transport processes, etc.It was found that in many modern plasma technologies, due to the interaction of the plasma with the material surfaces macroscopic particles from the material fall into the plasma (sizes are from micron fractions up to a few hundred microns). As result complex plasma is formed. The most common name of this plasma is dusty plasma. An interesting fact is that the dusty plasma forms under certain conditions the ordered structures ("plasma crystal", clouds, droplets). All of these plasma- dust structures are naturally occurring undesirable contamination and negatively affect on the physical and mechanical properties (microhardness, corrosion resistance, etc.) of the constructional materials.One of the most important scientific and technological problems is the realization of the controlled thermonuclear fusion. Formed in the wall region of the Tokamak dusty plasma can play a big role: recent experimental data show that the presence of dust in the plasma can affect the global energy confinement time. The use of the dusty plasma in the production of high composite materials is new field of application, for example, small spherical particles with nanocoating deposited in the plasma. In order to study formation of a homogeneous powder of the dust particles with desired properties and stability of its production, it is necessary to find the optimal conditions and time of production. Thus, the study of dusty plasma properties, their diagnostics are very important tasks, both from the scientific and applied aspects.

Reducing anthropogenic carbon dioxide emissions from coal-fired power plants is an important step in mitigating climate change. To implement carbon dioxide capture technologies, materials capable of removing carbon dioxide efficiently are required. Currently, liquid amine technology is used for carbon dioxide capture. However, the mechanism for carbon dioxide removal in liquid amine requires extraordinary amounts of energy input. Alternatively, solid sorbents such as metal-organic frameworks (MOFs) show promising potentials as a type of material for carbon dioxide capture. Due their varying structural properties, MOFs can be configured for specific purposes. Certain MOFs carry a net charge on their frameworks, which may allow for increased interactions with carbon dioxide molecules. In this work, charged MOFs were studied for their potential in carbon dioxide capture. Due to the massive number of MOFs available, computational methods were employed for the study. This project includes three major components: (1) the development of novel computational methods to simulate the gas adsorption properties in charged materials, (2) a diverse database of 47,244 hypothetical charged MOFs was constructed to represent the capabilities of charged MOFs, and (3) screening of high performing charged MOFs for carbon capture application by combining the previous two portions of the project. The methods developed in this work include fitting intermolecular interaction parameters to quantum mechanical calculations in periodic systems with net charges. No methods have been reported in literature for such parameter fittings, even in well studied materials such as zeolites. Therefore, the gas adsorption estimation method for charged materials developed in this work is proprietary. Also, databases of hypothetical MOFs with framework net charges have never been reported previously in literature. By screening the charged MOFs in the database with the methods developed, gas adsorption capabilities were evaluated. The adsorption properties of a neutral group of hypothetical MOFs were also obtained for a baseline comparison. Between the two groups of MOFs, charged MOFs were found to outperform neutral MOFs in three key aspects. Firstly, charged MOFs were able to adsorb an average of three times as much carbon dioxide than the neutral group. Secondly, charged MOFs were capable of removing twice the amount of carbon dioxide per adsorption/desorption cycle than the neutral MOFs. Lastly, charged MOFs were able to selectively adsorb much more carbon dioxide over other gasses present in the carbon dioxide capture situations. Specific structural features that resulted in the selectiveness of adsorption in charged MOFs were identified. Also, positive correlations were found between the adsorption of carbon dioxide and the charge present in the MOFs. As seen in the results, charges present in MOFs can greatly increase their ability to remove carbon dioxide. Charged MOFs in the hypothetical database not only outperformed neutral MOFs, certain top performers were also found to exceed the requirements for post-combustion carbon capture application. Therefore, charged MOFs were shown to be a possible material for future carbon dioxide capture. The proprietary methods developed in this work can not only be used to simulate gas adsorptions in charged MOFs, but also for other porous materials, regardless of net charges presented in their systems. Also, the database constructed in this work can be utilized in multiple ways. Aside from carbon dioxide capture capabilities, the charged MOFs in the database can be screened for other gas separations and catalysis via high throughput screening. The database and the computational methods developed in this work pave the way for discovering the capabilities of charged materials.

Theoretical part of this thesis is dedicated to the theoretical basis of electric conduction phenomena in fluids and method of calculation of magnetohydrodynamic phenomena. In the experimental part, computational modules have been developed to complement and augment the use of commercial simulation programs for simulation in the field of magnetohydrodynamics. On practical examples of mass spectrometer simulation, Einzel lens, electron movement and electric circuit breaker, the functionality of the computational models and the correctness of the obtained results were documented. Created computational modules can be used to design and optimize products using magnetohydrodynamic phenomena.

In dieser Arbeit wird die Erzeugung permanenter Nanostrukturen durch den Beschuss mit langsamen (v < 5x105m/s) hochgeladenen (q < 40) Ionen auf den Oberflächen der Ionenkristalle CaF2 sowie KBr untersucht. Die systematische Analyse der Probenoberfläche mittels Raster-Kraft-Mikroskopie liefert detaillierte Informationen über den Einfluss von potentieller und kinetischer Projektilenergie auf den Prozess der Strukturerzeugung. Der individuelle Einfall hochgeladener Ionen auf der KBr(001)-Oberfläche kann die Erzeugung monoatomar tiefer, lochartiger Strukturen -Nanopits- mit einer lateralen Ausdehnung von wenigen 10nm initiieren. Das Volumen dieser Löcher und damit die Anzahl gesputterter Sekundärteilchen zeigt eine lineare Abhängigkeit von der potentiellen Energie der Projektile. Für das Einsetzen der Locherzeugung konnte ein von der Projektilgeschwindigkeit abhängiger Grenzwert der potentiellen Energie E_grenz^pot (Ekin) gefunden werden. Auf der Basis der defekt-induzierten Desorption durch Elektronen wurde unter Einbeziehung von Effekten der Defektagglomeration ein konsistentes mikroskopisches Modell für den Prozess der Locherzeugung konzipiert. Für die CaF2(111)-Oberfläche kann die aus jüngsten Studien bekannte, individuelle Erzeugung hügelartiger Nanostrukturen -Nanohillocks- durch hochgeladene Ionen in dieser Arbeit auch für kleinste kinetische Energien (E_kin < 150eVxq) verifiziert werden. Die potentielle Energie der einfallenden Ionen wird damit erstmalig zweifelsfrei als alleinige Ursache der Nanostrukturerzeugung identifiziert. Zudem zeigt sich bei geringer Projektilgeschwindigkeit eine Verschiebung der potentiellen Grenzenergie zur Hillock-Erzeugung. Im Rahmen einer Kooperation an der Technischen Universität Wien durchgeführte Simulationsrechnungen auf der Grundlage des inelastischen thermal spike-Modells zeigen, dass die individuelle Hillock-Erzeugung durch hochgeladene Ionen mit einer lokalen Schmelze des Ionenkristalls verknüpft werden kann. Dem essentiellen Einfluss der Elektronenemission während der Wechselwirkung des hochgeladenen Ions mit der Oberfläche auf den Prozess der Nanostrukturerzeugung wird in komplementären Untersuchungen zur Sekundärelektronenstatistik Rechnung getragen. Erstmalig werden dabei Gesamtelektronenausbeuten für Isolatoroberflächen bei kleinsten Projektilgeschwindigkeiten (v < 1x10^5 m/s) bestimmt. Für Geschwindigkeiten v < 5x10^4 m/s findet sich für die Isolatoroberfläche in starkem Kontrast zu Metallen ein signifikanter Abfall der Elektronenausbeute mit sinkender kinetischer Energie. Mögliche Ursachen dieses Effektes werden auf der Grundlage unterschiedlicher Modelle diskutiert.

The purpose of this bachelor thesis was to investigate how charged groups within the pulp fibre affect the beatability and the strength of the papers. To obtain different levels of charges on the pulp it was carboxymethylated. The different pulp samples were beaten to different degrees to investigate how charges interact with the beating. A PFI-mill was used for the beating because of the relatively homogenous effect on the fibres and the low demand for pulp fibres for each beating. The influence of the amount of charged groups on the surface and bulk swelling, as a result of the beating process, was evaluated.   The fibres were then analysed in a Fibre tester and using a microscope to see what had happened to the fibre structure.  The results showed that the PFI-mill mainly affects the surface of the fibres. The beatability, defined as the swelling obtain for a specific energy input, was greatly increased by the introduction of charges. It was also shown that there is a possibility to replace some of the energy input in the mill with the introduction of charges to obtain the same swelling and strength.   Paper sheets were formed from the different samples and some mechanical properties were analyzed. It was shown that the strength was initially improved by the introduction of charges but the improvement was partially lost during the beating. At the highest rate of beating the difference in strength between the samples had disappeared. This can be explained by the fact that the fibres, from the sample with highest number of charges, were destroyed. Microscopic images showed that the fibre was delaminated and at some sites there were extreme balloon-like swellings / Syftet med detta examensarbete var att undersöka hur laddade grupper hos massafibrer påverkar malbarheten och styrkan hos de papper som tillverkats av dessa fibrer. För att skapa olika laddningsnivåer karboxymetylerades viss del av massan för att introducera laddade grupper, två delar av ursprungsmassan karboxymetylerades och en del användes som referensmassa.  De olika massaproverna maldes i olika nivåer för att undersöka hur laddningarna och malningen interagerade. En PFI-kvarn användes för att mala fibrerna då det endast krävs små mängder fibrer och denna typ av kvarn påverkar fibrerna relativt homogent. Fibrerna analyserades sedan i en Fibre tester och med ett mikroskop för att se vad som hade hänt med fiberstrukturen. Resultaten visade att en PFI-kvarn till största delen påverkar fibrernas yta.  Malbarheten, som definierades som den svällning som åstadkoms vid en viss energiinsats i form av malvarv i kvarnen, ökades markant då ytterligare laddningar fanns närvarande i fibrerna. Det visades också att det går att ersätta en del av malningen med introduktion av laddningar till fibrerna för att uppnå samma svällning och styrka. Pappersark tillverkades därefter av de olika massatyperna och några mekaniska egenskaper testades. Det visades att styrkan ökades initialt av introduktionen av laddningar men denna förbättring minskade vid malningen. Vid den högsta malgraden hade skillnaden mellan de olika massorna försvunnit. Det kan förklaras av att fibrerna, från den massatyp med mest laddningar, hade förstörts. På vissa ställen hade fibern helt delaminerats och extrema ballonglika svällningar fanns.

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Chemistry is the study of materials and the changes that materials undergo. One can tune the properties of the known materials and design the novel materials with desired properties knowing what is responsible for the chemical reactivity, structure, and stability of those materials. The unified chemical bonding theory could address all these questions, but we do not have one available yet. The most accepted general theory of chemical bonding was proposed by Lewis in 1916, though Lewis’s theory fails to explain the bonding in materials with delocalized electron density such as sub-nano and nanoclusters, as well as aromatic organic and organometallic molecules. The dissertation presents a set of projects that can be considered the steps towards the development of the unified chemical bonding theory by extending the ideas of Lewis. The dissertation also presents the studies of the properties of multiply charged anions, which tend to undergo Coulomb explosion in the isolated state and release the excess energy stored in them. It is shown how the properties of multiply charged anions can be tuned upon changing the chemical identity of the species or interaction with solvent molecules. Our findings led to the discovery of a new long-lived triply charged anionic species, whose metastability was explained by the existence of a repulsive Coulomb barrier. We also proposed two ways to restore high symmetry of compounds by suppression of the pseudo Jahn-Teller effect, which could lead to the design of new materials with the restored symmetry and therefore the novel properties.