Gas-phase electron diffraction (GED) is the only viable technique for the accurate structural study of gas-phase molecules that contain more than ~10 atoms. Recent advances in Edinburgh have made it possible to study larger, more complex, stable molecules using the SARACEN method. This thesis is concerned with obtaining the structures of unstable species, using both standard GED techniques and by developing a new method in which ash vacuum pyrolysis is used to generate short-lived species in situ. In the first part of this thesis nine primary phosphines (R-PH2) with different substituents (R = methyl, vinyl, ethynyl, allenyl, allyl, propargyl, phenyl, benzyl and chloromethyl) are studied by GED. Vinylarsine and vinyldichloroarsine are also studied. Primary phosphines and arsines appear infrequently in the literature owing to their toxicity and high reactivity, especially of the unsaturated systems. The conformational behaviour in these molecules and trends throughout the series are rationalised. As appropriate, comparisons are made to analogous amines and the differences found are discussed. Tertiary phosphines (R3P) are routinely protected by complexation with borane (BH3) and it has been proposed that this technique could be extended to primary phosphines. As an extension of the initial investigation, the GED study of methylphosphine-borane offers an insight into structural changes that occur upon complexation, although attempts to study larger phosphine-borane complexes by GED proved dificult. The structures and bonding trends in a series of phosphineborane adducts are discussed, mainly using the results of ab initio calculations. The second part of the thesis details the implementation of a new, very high temperature nozzle, which allows the generation of short-lived species by pyrolysis. The workings of this nozzle are discussed and the study of the structure of ketene, generated from three different precursors, is detailed. The benzyl radical has also been studied, and a preliminary GED structure is presented. As a result of this work the molecular structures of Meldrum's acid and dibenzylsulfone are also presented, having been determined in the gas phase for the first time.

We present and explore a new formulation of perturbative QCD based not on the renormalised coupling but on the dimensional transmutation parameter of the theory and the property of asymptotic scaling. The approach yields a continued function, the iterated function being that involved in the solution of the two-loop β-function equation. In the so-called large-b limit the continued function reduces to a continued fraction and the successive approximants are diagonal Padé approximants. We investigate numerically the convergence of successive approximants using the leading-b approximation, motivated by renormalons, to model the all-orders result. We consider the Adler D-function of vacuum polarisation, the Polarised Bjorken and Gross-Llewellyn Smith sum rules, the (unpolarised) Bjorken sum rule, and the Minkowskian quantities R(_r) and the R-ratio of e(^+)e(^-) annihilation. In contrast to diagonal Fade approximants the truncated continued function method gives remarkably stable large-order approximants in cases where infra-red renormalon effects are important. We also use the new approach to determine the QCD fundamental parameters from the R(_r) and the R-ratio measurements, where we find Ā(^(3))(_MS)=516±48 MeV (which yields a(_s)(µ=m(_r))=0.360(^+0.021)(_=0.020)), and Ā(^(5))(_MS)=299(^+6)(_-7) MeV (which yields a(_s)(µ=m(_zo)=0.1218±0.0004), respectively. The evolution of the former value to the m(_zo) energy results in a(_s)(µ= m(_zo)) = 0.123 ± 0.002. These values are in line with other determinations available in the literature. We implement the Complete Renormalisation Group Improvement (CORGI) scheme throughout all the calculations. We report on how the mathematical concept of Stieltjes series can be used to assess the convergence of Padé approximants of perturbative series. We find that the combinations of UV renormalons which occur in perturbative QCD may or may not be Stieltjes series depending on the renormalisation scheme used.

<p>This dissertation consists of two independent musical compositions and an article detailing the process of the design and assembly of an electric guitar with particular emphasis on the carefully curated suite of embedded effects. </p><p>The first piece, 'Phase Locked Loop and Modulo Games' is scored for electric guitar and a single echo of equal volume less than a beat away. One could think of the piece as a 15 minute canon at the unison at the dotted eighth note (or at times the quarter or triplet-quarter), however the compositional motivation is more about weaving a composite texture between the guitar and its echo that is, while in theory extremely contrapuntal, in actuality is simply a single [superhuman] melodic line.</p><p>The second piece, 'The Dogma Loops' picks up a few compositional threads left by ‘Phase Locked Loop’ and weaves them into an entirely new tapestry. 'Phase Locked Loop' is motivated by the creation of a complex musical composite that is for the most part electronically transparent. 'The Dogma Loops' questions that same notion of composite electronic complexity by essentially asking a question: "what are the inputs to an interactive electronic system that create the most complex outputs via the simplest musical means possible?"</p><p>'The Dogma Loops' is scored for Electric Guitar (doubling on Ukulele), Violin and Violoncello. All of the principal instruments require an electronic pickup (except the Uke). The work is in three sections played attacca; [Automation Games], [Point of Origin] and [Cloning Vectors]. </p><p>The third and final component of the document is the article 'Finding Ibrida.' This article details the process of the design and assembly of an electric guitar with integrated effects, while also providing the deeper context (conceptual and technical) which motivated the efforts and informed the challenges to hybridize the various technologies (tubes, transistors, digital effects and a microcontroller subsystem). The project was motivated by a desire for rigorous technical and hands-on engagement with analog signal processing as applied to the electric guitar. ‘Finding Ibrida’ explores sound, some myths and lore of guitar tech and the history of electric guitar distortion and its culture of sonic exploration.</p> / Dissertation

<p>Carbon nanotubes (CNTs) have recently emerged as promising candidates for electron field emission (FE) cathodes in integrated FE devices. These nanostructured carbon materials possess exceptional properties and their synthesis can be thoroughly controlled. Their integration into advanced electronic devices, including not only FE cathodes, but sensors, energy storage devices, and circuit components, has seen rapid growth in recent years. The results of the studies presented here demonstrate that the CNT field emitter is an excellent candidate for next generation vacuum microelectronics and related electron emission devices in several advanced applications.</p><p> The work presented in this study addresses determining factors that currently confine the performance and application of CNT-FE devices. Characterization studies and improvements to the FE properties of CNTs, along with Micro-Electro-Mechanical Systems (MEMS) design and fabrication, were utilized in achieving these goals. Important performance limiting parameters, including emitter lifetime and failure from poor substrate adhesion, are examined. The compatibility and integration of CNT emitters with the governing MEMS substrate (i.e., polycrystalline silicon), and its impact on these performance limiting parameters, are reported. CNT growth mechanisms and kinetics were investigated and compared to silicon (100) to improve the design of CNT emitter integrated MEMS based electronic devices, specifically in vacuum microelectronic device (VMD) applications.</p><p> Improved growth allowed for design and development of novel cold-cathode FE devices utilizing CNT field emitters. A chemical ionization (CI) source based on a CNT-FE electron source was developed and evaluated in a commercial desktop mass spectrometer for explosives trace detection. This work demonstrated the first reported use of a CNT-based ion source capable of collecting CI mass spectra. The CNT-FE source demonstrated low power requirements, pulsing capabilities, and average lifetimes of over 320 hours when operated in constant emission mode under elevated pressures, without sacrificing performance. Additionally, a novel packaged ion source for miniature mass spectrometer applications using CNT emitters, a MEMS based Nier-type geometry, and a Low Temperature Cofired Ceramic (LTCC) 3D scaffold with integrated ion optics were developed and characterized. While previous research has shown other devices capable of collecting ion currents on chip, this LTCC packaged MEMS micro-ion source demonstrated improvements in energy and angular dispersion as well as the ability to direct the ions out of the packaged source and towards a mass analyzer. Simulations and experimental design, fabrication, and characterization were used to make these improvements.</p><p> Finally, novel CNT-FE devices were developed to investigate their potential to perform as active circuit elements in VMD circuits. Difficulty integrating devices at micron-scales has hindered the use of vacuum electronic devices in integrated circuits, despite the unique advantages they offer in select applications. Using a combination of particle trajectory simulation and experimental characterization, device performance in an integrated platform was investigated. Solutions to the difficulties in operating multiple devices in close proximity and enhancing electron transmission (i.e., reducing grid loss) are explored in detail. A systematic and iterative process was used to develop isolation structures that reduced crosstalk between neighboring devices from 15% on average, to nearly zero. Innovative geometries and a new operational mode reduced grid loss by nearly threefold, thereby improving transmission of the emitted cathode current to the anode from 25% in initial designs to 70% on average. These performance enhancements are important enablers for larger scale integration and for the realization of complex vacuum microelectronic circuits.</p> / Dissertation

Microwave hydrodiffusion and gravity (MHG) technique is an attempt towards development of green extraction, as this environment friendly technique has completely eliminated the use of organic solvents. After describing the effectiveness of microwave radiations in extraction field in the first part of this manuscript, we have optimized this noval extraction method to get antioxidants rich extract. Along with studying the temperature distributions in different parts of plant material under the effect of microwave irradiations, we have analyzed the influence of microwaves in enhancing the antioxidant activity of extracts by using different tests. We have got the promising results concerning about the antioxidant rich extracts of different onion varieties and sea buckthorn in generalization step against the conventional solvent extracts. The application of vacuum system in this extraction system helped in restraining the limitations like dry extract yield and flavonol contents. Incomparison to traditional and recent extraction systems, the MHG extracts doesn’t require any filtration and purification steps as it works in absence of any solvent and water and are highly recommended for direct application in industrial products / L'hydrodiffusion générée par micro-ondes est une nouvelle technique d'extraction mise au point au sein de l'Université d'Avignon et des Pays de Vaucluse. Ce procédé est une combinaison entre une technique traditionnelle et une technologie innovante. En effet, le chauffage par micro-ondes a permis d'initier et de générer le transfert de matière et de chaleur de l"intérieur des matrices végétales (oignons) vers l'extérieur et de réduire de façon considérable les temps d'extraction des antioxydants sans aucune intervention de solvant. A titre de comparaison, les polyphénols de différentes variétés d'oignons ont été extraits par l'hydrodiffusion générée par micro-ondes et par la technique conventionnelle, l'extraction par solvant. Les rendements obtenus par micro-ondes sont presque identiques à ceux obtenus à l'aide d’un solvant alors que les temps d'extraction sont réduits. La capacité antioxydante des extraits micro-ondes est supérieure à celle obtenue par technique conventionelle. Ce qui présage des potentialités d'application dans le domaine agroalimentaire en particulier pour la valorisation des co-produits. Une étude cinétique de l'extraction, ainsi qu'une observation au microscope optique(cytologie) des matrices traitées soumises aux micro-ondes et au solvant ont mis en évidence la spécificité de l'extraction sans solvant assistée par micro-ondes au niveau des mécanismes de libération et d'extraction des molécules antioxydantes au sein du végétal. L'effet des micro-ondes a pour conséquence une libération plus rapide des principes actifs contenue dans la plante grâce à l'ouverture quasi instantanée des glandes et l'explosion des cellules. L'explication de la différence de composition chimique entre les procédés d'extraction par solvant et par micro-ondes pourrait être basée principalement sur des phénomènes de solubilité, de polarisation diélectrique ainsi qu'un transfert de matière et de chaleur inversé

The hydrogenation of β-ketoesters over chirally modified Ni catalysts is a celebrated and thoroughly researched example of an enantioselective heterogeneous catalytic reaction. Enantioselective heterogeneous processes, although extremely attractive in terms of fewer complications in the separation of products from the catalyst, are hindered in their viability as industrial applications due to the lack of detailed knowledge on how chirality is conferred to the metal surface. Surface science techniques have afforded substantial progress into determining mechanisms between modifier, reactant and catalyst to explain the source of enantioselectivity of the system. In this study, a combination of solution and ultra-high vacuum (UHV)-based experiments allow a more realistic interpretation of the surface chemistry underpinning the catalytic reaction as the key step in achieving enantioselective performance is the adsorption of chiral modifiers from solution. The behaviour of (S)-aspartic acid and (S)-lysine on Ni{111} and their interaction with the prochiral β-ketoester methylacetoacetate is investigated in this study to understand their potential as chiral modifiers for the system. In UHV, scanning tunnelling microscopy (STM), reflection absorption infrared spectroscopy (RAIRS), and temperature programmed desorption (TPD) are used to analyse the conformation and order of the amino acids on the metal, and their thermal stability. Additionally, liquid-solid interface RAIRS and X-ray photoelectron spectroscopy (XPS) are used to examine the modified Ni surface, prepared under aqueous conditions, to give an accurate representation of the catalytic studies. It has been found highly likely that, for (S)-aspartic acid modified Ni{111}, enantioselective sites exist at step or step/kink defects, formed by corrosive leaching of the Ni substrate. Conversely, lysine appears to bind with a high sticking probability to Ni, in the form of lysine islands, and does not appear to etch the Ni chirally. Finally, similar experiments have been carried out on Au{111}, where lysine was found to chiral restructure the surface and form nanofingers, and 2D Ni clusters grown on Au{111} in order to investigate the formation of possible metal-organic frameworks.

Einstein's equations in vacuum spacetimes with two spacelike killing vectors are explored using affine projection tensor geometry. By doing a semi-conformal transformation on the metric, a new "fiducial" geometry is constructed using a projection tensor fields. This fiducial geometry provides coordinate independent information about the underlying structure of the spacetime without the use of an explicit form of the metric tensor.

Purpose: This study analyzed the percentage of Virginia practitioners utilizing vacuum form machines, types of appliances recommended, and types of patient information provided.Methods: Questionnaires were constructed and mailed to 2500 dentists.Results: 80% of dentists utilized vacuum form machines, 42.5% recommended mouthguards, 60.2% recommended home bleaching trays, 37.6% provided patient information on mouthguards, 37.1% provided patient information on home bleaching trays, 16.5% inquired on patient questionnaires about mouthguard protection during contact sports,and 17.3% inquired on patient questionnaires about tooth color satisfaction.Conclusions: Dentists use vacuum form machines for home bleaching trays more than mouthguards. General dentists and pediatric dentists provide patient information on mouthguards and home bleaching trays more often than orthodontists. General dentists provide patient information on home bleaching trays more often than pediatric dentists. Dentists in practice 25 or more years are the most likely to have patient questionnaires that address the use of mouthguards.

In the present work the vacuum polarization and the circular dichroism of hydrogen-like atoms are studied. We derive equations for the Fourier transforma- tion of the vacuum expectation value of the charge density. We use it to derive Uehling potential and calculate energy shifts caused by it. Then we discuss effects of vacuum polarization in higher orders of α. In second part we define circular dichroism and we express it in terms of reduced matrix elements. Then we derive the formula for parity vilating potential which is generated by weak interaction and together with other results we use it to find the expression for circular dichro- ism in terms of hydrogen radial functions. 1

Title: Instantons and Unitarily Inequivalent Quantum Vacua Author: Roman Derco Department: Institute of Particle and Nuclear Physics Supervisor: doc. Alfredo Iorio, Ph.D., Institute of Particle and Nuclear Physics Abstract: In the presented thesis we investigate the relationship between the topologically distinct instantonic vacua and the unitarily inequivalent vacua of the quantum field theory. We focus on quantum mechanical exam- ples, where instantons appear but the complications due to quantum gauge field theory are absent. A model for quantum dissipation and the theory of one particle escaping from a metastable minimum were compared, what led to some observations. A double well system was build from harmonic oscillators and an interaction term to get closer to the quantum dissipation model, where inequivalent representations are involved. We identified the particularly simple model of a quantum particle constrained on a circle to be the ideal toy model for spotting the relation among unitarily inequivalent vacua and topologically distinct vacua we were seeking for. 1