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The DART ion source was introduced in 2005 at the ASMS Sanibel Conference and immediately afterward Professor Sparkman was contemplating of a way to get our lab this revolutionary mass spectrometry ionization technique. It did not take long because it was delivered to the Pacific Mass Spectrometry Facility in August 2006 and I was able to being using and learning the technique. The ion source creates excited state helium metastables (2 3 S) with an ionization potential of 19.8 eV are created by a glow discharge at atmospheric pressure. The metastables are sent through an optional heater, to aid in desorption, enter the open-air to directly ionize your sample or ionize reagent species to react with the analyte molecules. The most observed ionization mechanism is the formation of protonated molecules from a proton-transfer reaction between the analyte and protonated water clusters. The limited to no sample preparation with the "soft" ionization provide very quick identification of intact organic ions in or on various types of matrices. When the DART is coupled to a high resolving power instrument, such as the JEOL AccuTOF, accurate masses and accurate isotope ratios are assigned to aid in the determination of unknown elemental compositions. This research discusses the formation of the metastable species and how they are used to produce analyte and reagent ions within the open-air sample gap of the DART-mass spectrometer interface. A description of the fundamentals on the operation including real time visualization of the fluid dynamics and confirmation of the formation of a hydroxyl radical in the proposed formation of the protonated water clusters, along with applications developed in the Pacific Mass Spectrometry Facility will also be discussed. These include cleavage, desorption, and ionization of solid-phase peptides, desorption of aqueous metal ions using a heated wire filament and the increased ion transmission with the Vapur interface using metal coated glass tube for the transfer tube.

Aggregate aus Molekülen, in denen die Moleküle über ihre elektronischen Übergangsdipole miteinander wechselwirken, finden wegen ihrer besonderen optischen und Energietransfer-Eigenschaften vielfach Anwendung in Natur, Technik, Biologie und Medizin. Beispiele sind die wechselwirkenden Farbstoffmoleküle, die in den Lichtsammelkomplexen Photosynthese betreibender Lebewesen Sonnenlicht absorbieren und die Energie als elektronische Anregung hocheffizient zu Reaktionszentren weiterleiten, oder Aggregate aus tausenden von organischen Farbstoffmolekülen in einem flüssigen Lösungsmittel. Die Wechselwirkung der Moleküle (Monomere) führt zu über mehrere Moleküle delokalisierten angeregten elektronischen Zuständen, die die Energietransfer-Dynamik und die Absorptionsspektren der Aggregate prägen. Die Lichtabsorption und der Energietransfer in molekularen Aggregaten werden oft stark von Vibrationen beeinflusst, sowohl von internen Vibrationsfreiheitsgraden der Monomere als auch von Vibrationen der Umgebung (z. B. das Proteingerüst in Lichtsammelkomplexen oder eine Flüssigkeitsumgebung), an die die elektronische Anregung koppelt. Da es schwierig ist, diese Vibrationen in die theoretische Beschreibung des Transfers und der Spektren einzubeziehen, ist ihr genauer Einfluss noch nicht gut verstanden. Um dieses Verständnis zu verbessern, entwickeln wir in dieser Arbeit neue Berechnungsmethoden und untersuchen damit die Auswirkungen der Vibrationen. Zuerst betrachten wir die diskreten internen Vibrationsfreiheitsgrade der Monomere. Dazu haben wir eine effiziente numerische Methode entwickelt, die es uns erlaubt, mehrere Freiheitsgrade pro Monomer explizit einzubeziehen und die volle Schrödinger-Gleichung zu lösen. Mit den Modellrechnungen können wir experimentelle Aggregat-Spektren der Helium-Nanotröpfchen-Isolation-Spektroskopie, mit der man die einzelnen Vibrationslinien der Monomere auflösen kann, zum ersten Mal quantitativ reproduzieren. In früheren theoretischen Behandlungen wurde oft nur ein einziger Vibrationsfreiheitsgrad pro Monomer berücksichtigt – nun zeigen wir, dass die Einbeziehung möglichst vieler Freiheitsgrade für eine realistische Beschreibung von Aggregat-Spektren wichtig ist. Um neben den internen Vibrationen auch den Einfluss der Umgebung beschreiben zu können, nutzen wir den Zugang offener Quantensysteme und nehmen an, dass die elektronische Anregung an ein strukturiertes Kontinuum von Vibrationsfreiheitsgraden koppelt. Erstmals wenden wir die sogenannte nicht-markovsche Quanten-Zustands-Diffusion auf die molekularen Aggregate an, wodurch wir mit Hilfe einer Näherung Spektren und Transfer mit einer sehr effizienten stochastischen Schrödinger-Gleichung berechnen können. So können wir Merkmale gemessener Aggregat-Spektren, wie das schmale J-Band und das breite strukturierte H-Band, in Abhängigkeit der Anzahl der Monomere und der Wechselwirkungsstärke zwischen den Monomeren beschreiben. Auch können wir den Übergang von kohärentem zu inkohärentem Transfer erfassen. Eine für den Transfer relevante Größe ist die Anzahl der kohärent gekoppelten Monomere im Aggregat. Diese schätzt man häufig aus der Verschmälerung des Aggregat-Spektrums ab. Wir finden jedoch für verschiedene Spektraldichten des Vibrationskontinuums sehr unterschiedliche Verschmälerungen des Aggregat-Spektrums, die wir analytisch erklären. So zeigen wir, dass die bisherige einfache Abschätzung der Anzahl der kohärent gekoppelten Monomere nicht gerechtfertigt ist, da die Verschmälerung stark vom angenommenen Modell abhängt.

Aggregate aus Molekülen, in denen die Moleküle über ihre elektronischen Übergangsdipole miteinander wechselwirken, finden wegen ihrer besonderen optischen und Energietransfer-Eigenschaften vielfach Anwendung in Natur, Technik, Biologie und Medizin. Beispiele sind die wechselwirkenden Farbstoffmoleküle, die in den Lichtsammelkomplexen Photosynthese betreibender Lebewesen Sonnenlicht absorbieren und die Energie als elektronische Anregung hocheffizient zu Reaktionszentren weiterleiten, oder Aggregate aus tausenden von organischen Farbstoffmolekülen in einem flüssigen Lösungsmittel. Die Wechselwirkung der Moleküle (Monomere) führt zu über mehrere Moleküle delokalisierten angeregten elektronischen Zuständen, die die Energietransfer-Dynamik und die Absorptionsspektren der Aggregate prägen. Die Lichtabsorption und der Energietransfer in molekularen Aggregaten werden oft stark von Vibrationen beeinflusst, sowohl von internen Vibrationsfreiheitsgraden der Monomere als auch von Vibrationen der Umgebung (z. B. das Proteingerüst in Lichtsammelkomplexen oder eine Flüssigkeitsumgebung), an die die elektronische Anregung koppelt. Da es schwierig ist, diese Vibrationen in die theoretische Beschreibung des Transfers und der Spektren einzubeziehen, ist ihr genauer Einfluss noch nicht gut verstanden. Um dieses Verständnis zu verbessern, entwickeln wir in dieser Arbeit neue Berechnungsmethoden und untersuchen damit die Auswirkungen der Vibrationen. Zuerst betrachten wir die diskreten internen Vibrationsfreiheitsgrade der Monomere. Dazu haben wir eine effiziente numerische Methode entwickelt, die es uns erlaubt, mehrere Freiheitsgrade pro Monomer explizit einzubeziehen und die volle Schrödinger-Gleichung zu lösen. Mit den Modellrechnungen können wir experimentelle Aggregat-Spektren der Helium-Nanotröpfchen-Isolation-Spektroskopie, mit der man die einzelnen Vibrationslinien der Monomere auflösen kann, zum ersten Mal quantitativ reproduzieren. In früheren theoretischen Behandlungen wurde oft nur ein einziger Vibrationsfreiheitsgrad pro Monomer berücksichtigt – nun zeigen wir, dass die Einbeziehung möglichst vieler Freiheitsgrade für eine realistische Beschreibung von Aggregat-Spektren wichtig ist. Um neben den internen Vibrationen auch den Einfluss der Umgebung beschreiben zu können, nutzen wir den Zugang offener Quantensysteme und nehmen an, dass die elektronische Anregung an ein strukturiertes Kontinuum von Vibrationsfreiheitsgraden koppelt. Erstmals wenden wir die sogenannte nicht-markovsche Quanten-Zustands-Diffusion auf die molekularen Aggregate an, wodurch wir mit Hilfe einer Näherung Spektren und Transfer mit einer sehr effizienten stochastischen Schrödinger-Gleichung berechnen können. So können wir Merkmale gemessener Aggregat-Spektren, wie das schmale J-Band und das breite strukturierte H-Band, in Abhängigkeit der Anzahl der Monomere und der Wechselwirkungsstärke zwischen den Monomeren beschreiben. Auch können wir den Übergang von kohärentem zu inkohärentem Transfer erfassen. Eine für den Transfer relevante Größe ist die Anzahl der kohärent gekoppelten Monomere im Aggregat. Diese schätzt man häufig aus der Verschmälerung des Aggregat-Spektrums ab. Wir finden jedoch für verschiedene Spektraldichten des Vibrationskontinuums sehr unterschiedliche Verschmälerungen des Aggregat-Spektrums, die wir analytisch erklären. So zeigen wir, dass die bisherige einfache Abschätzung der Anzahl der kohärent gekoppelten Monomere nicht gerechtfertigt ist, da die Verschmälerung stark vom angenommenen Modell abhängt.

Nanostructured ZnO films were obtained via thermal oxidation of thin films formed with metallic Zn-nanoparticle dispersions. Commercial zinc nanoparticles used for this work were characterized by microscopic and thermal analysis methods to analyze the Zn-ZnO core shell structure, surface morphology and oxidation characteristics. These dispersions were spin-coated on SiO₂/Si substrates and then annealed in air between 100 and 600 °C. Significant nanostructural changes were observed for the resulting films, particularly those from larger Zn nanoparticles. These nanostructures, including nanoneedles and nanorods, were likely formed due to fracturing of ZnO outer shell due to differential thermal expansion between the Zn core and the ZnO shell. At temperatures above 227 °C, the metallic Zn has a high vapor pressure leading to high mass transport through these defects. Ultimately the Zn vapor rapidly oxidizes in air to form the ZnO nanostructures. We have found that the resulting films annealed above 400 °C had high electrical resistivity. The zinc nanoparticles were incorporated into zinc indium oxide solution and spin-coated to form thin film transistor (TFT) test structures to evaluate the potential of forming nanostructured field effect sensors using simple solution processing. The functionalization of zinc tin oxide (ZTO) films with self-assembled monolayers (SAMs) of n-hexylphosphonic acid (n-HPA) was investigated. The n-HPA modified ZTO surfaces were characterized using contact angle measurement, x-ray photoelectron spectroscopy (XPS) and electrical measurements. High contact angles were obtained suggesting high surface coverage of n-HPA on the ZTO films, which was also confirmed using XPS. The impact of n-HPA functionalization on the stability of ZTO TFTs was investigated. The n-HPA functionalized ZTO TFTs were either measured directly after drying or after post-annealing at 140 °C for 48 hours in flowing nitrogen. Their electrical characteristics were compared with that of non-functionalized ZTO reference TFTs fabricated using identical conditions. We found that the non-functionalized devices had a significant turn-on voltage (V[subscript ON]) shift of ~0.9 V and ~1.5 V for the non-annealed and the post-annealed conditions under positive gate bias stress for 10,000 seconds. The n-HPA modified devices showed very minimal shift in V[subscript ON] (0.1 V), regardless of post-thermal treatment. The VON instabilities were attributed to the interaction of species from the ambient atmosphere with the exposed ZTO back channel during gate voltage stress. These species can either accept or donate electrons resulting in changes in the channel conductance with respect to the applied stress. / Graduation date: 2012 / Access restricted to the OSU Community at author's request from Jan. 6, 2012 - Jan. 6, 2013

This thesis describes investigations into the properties of -phase BEDT-TTF charge transfer salts. Charge transfer salts are mainly studied as they are very useful test beds for fundamental physics due to the tuneability of their proper- ties and ground states. The effects of temperature and pressure on such systems have been studied, as these allow access to a wide range of different states and properties. Transport properties of these systems have been studied to obtain information about the Fermi surface and effective mass, and the effect of deuter- ation and also change of pressure media will be discussed. The interaction of infrared radiation with these systems has also been investigated and simultaneous pressure and temperature measurements will be presented, something not greatly studied due to the large technical challenges. The techniques and approaches for overcoming these are also discussed. Chapter 1 provides an introduction to the organic materials themselves with particular emphasis on the actual compounds studied. Chapter 2 provides the necessary theoretical background for studying organic charge transfer salts using magnetic quantum oscillations and their infrared re- ectivity. Chapter 3 covers the experimental techniques and also discusses some of the challenges encountered and their solutions to aid others working in this area. Chapter 4 describes an investigation into the transport properties of - (ET)2Cu(SCN)2 by studying Shubnikov-de Haas oscillations using both deuter- ated and normal samples and using two different pressure media, and comparing it to work done using a third. Chapter 5 presents an investigation into the pressure dependence of selected phonon modes in -(ET)2Cu(SCN)2 using infrared radiation on a deuterated sam- ple. Chapter 6 presents what is believed to be the first pressure and temperature dependent infrared study of an organic molecular material. In this case the or- ganic molecular material is d8--(ET)2Cu[N(CN)2]Br, but the techniques should be readily transferable to other materials.

De nouveaux modèles d'atmosphère sont présentés, incluant les profils de raie d'hélium neutre améliorés de Beauchamp (1995) et le formalisme de probabilité d'occupation pour ce même atome. Ces modèles sont utilisés pour calculer une grille de spectres synthétiques correspondant à des atmosphères riches en hélium et contenant des traces d'hydrogène. Cette grille est utilisée pour déterminer les paramètres atmosphériques principaux des étoiles de notre échantillon, soient la température effective, la gravité de surface et l'abondance d'hydrogène. Notre échantillon contient des spectres visibles de haut rapport signal-sur-bruit pour 102 naines blanches riches en hélium, dont 29 ont été observés au cours de ce projet, ce qui en fait le plus grand échantillon de spectres de qualité de naines blanches riches en hélium. Des spectres synthétiques ont été calculés en utilisant différentes valeurs du paramètre α de la théorie de la longueur de mélange dans le but de calibrer empiriquement la valeur de ce paramètre pour les DB. Afin d'améliorer la précision sur les paramètres atmosphériques de quelques étoiles, nous avons utilisé des spectres couvrant la raie Hα pour mieux déterminer l'abondance d'hydrogène. Finalement, nous avons calculé la distribution de masse de notre échantillon et la fonction de luminosité des DB. La distribution de masse montre une coupure à 0.5 fois la masse solaire qui est prédite par les modèles d'évolution stellaire et dévoile une masse moyenne significativement plus élevée pour les étoiles de type DBA. La masse moyenne de l'ensemble des DB et DBA est très proche de celle des DA. La fonction de luminosité nous permet de calculer que le rapport du nombre de DB sur le nombre de DA vaut environ 25%. / New model atmospheres are presented, including improved neutral helium lines from Beauchamp (1995) and the occupation probability formalism for that atom. These models are used to compute a grid of synthetic spectra for helium rich atmospheres with different hydrogen abundances. This grid is used to determine the principal atmospheric parameters of the stars in our sample, e.g. effective temperature, surface gravity and hydrogen abundance. There are 102 high quality spectra of helium-rich white dwarfs in our sample, making it the largest sample of this kind. 29 of these spectra were observed for this project. Synthetic spectra using different values of the α parameter from the mixing length theory have been calculated in order to determine the correct value of this parameter for DB model atmospheres. Finally, we have computed the mass distribution of our sample and the DB luminosity funtion. The mass distribution shows a clear cutoff at 0.5 solar masses which is predicted by stellar evolution theory and gives a significantly higher mean mass for the DBA stars of the sample. However, the global mean mass of our sample is very close to that of DA stars. With our luminosity function, we found a number ratio of DB stars over DA stars of about 25%.

Uma nova metodologia para a medida absoluta da fração efetiva de nêutrons atrasados βeff, baseada em técnicas de análise de ruído microscópico e no modelo de Duas- Regiões, foi desenvolvida no reator IPEN/MB-01. Diferentemente das demais técnicas, tais como o Método de Bennet Modificado, o Método do Número de Nelson e o Método da fonte de 252Cf, a principal vantagem da metodologia proposta é a obtenção de βeff de um modo puramente experimental, sem a necessidade de quaisquer outros parâmetros, sejam estes calculados ou provenientes de outros experimentos. Com a finalidade de validar este novo método, uma série de experimentos Rossi-α e Feynman-α foram realizados no reator IPEN/MB-01. De acordo com a metodologia proposta, βeff foi estimado com uma incerteza de 0.67%, a qual atende aos requisitos de precisão almejados. Além disso, o tempo de geração de nêutrons prontos , dentre outros parâmetros, também foi obtido experimentalmente via esta metodologia. Em geral, os parâmetros medidos estão em acordo com resultados provenientes de experimentos de análise de ruído macroscópico. Nas comparações teoria-experimento, os valores de βeff medidos neste trabalho mostram que a biblioteca JENDL3.3 apresenta a melhor performance (dentro de 1%). Esta concordância justifica a redução no yield de fissão do 235U proposta por Sakurai e Okajima. / A new method for absolute measurement of the effective delayed neutron fraction, βeff , based on microscopic noise experiments and the Two-Region Model was developed at the IPEN/MB-01 Research Reactor facility. In contrast with other techniques like the Modified Bennet Method, Nelson-Number Method and 252Cf-Source Method, the main advantage of this new methodology is to obtain the effective delayed neutron parameters in a purely experimental way, eliminating all parameters that are difficult to measure or calculate. In this way, Rossi-α and Feynman-α experiments for validation of this method were performed at the IPEN/MB-01 facility, and adopting the present approach, βeff was measured with a 0.67% uncertainty. In addition, the prompt neutron generation time, , and other parameters were also obtained in an absolute experimental way. In general, the final results agree well with values from frequency analysis experiments. The theory-experiment comparison reveals that JENDL-3.3 shows deviation for βeff lower than 1% which meets the desired accuracy for the theoretical determination of this parameter. This work supports the reduction of the 235U thermal yield as proposed by Okajima and Sakurai.

O objetivo deste trabalho e a determinação dos coeficientes de viscosidade de cisalhamento e condutividade térmica de gases ideais quânticos. No cálculo dos coeficientes de transporte foram considerados dois aspectos: uma estatística quântica com seções transversais quânticas e uma estatística quântica com seções transversais quânticas. No primeiro caso, e utilizado um método alternativo para a determinação das aproximações sucessivas (ate a quinta ordem) para os coeficientes de transporte dos gases Helio 4, Helio 3, para-hidrogênio e orto-hidrogênio. No caso de estatística quântica desenvolvida uma teoria com base no método dos momentos de Grad e na equação de Uehling- Uhlenbeck, com a finalidade de determinar as express6es algébricas para os coeficientes de transporte. Esta teoria e baseada em 13 momentos, de densidade, velocidade, tensor pressão e fluxo de calor. Do conhecimento da função de distribuição em termos dos momentos, as equações constitutivas são determinadas e os coeficientes de transporte seguem de um método iterativo semelhante ao procedimento Maxwelliano. / The aim of this work is the determination of the coefficients of shear viscosity and thermal conductivity of quantum ideal gases. In the calculation of the transport coefficients two aspects have been taken into account: a classical statistical with quantum cross-sections and a quantum statistical with quantum cross-sections. In the first case, an alternative method is used for the determination of the successive approximations (up to the fifth order) to the transport coefficients of the gases helium 4, helium 3, para-hydrogen, ortho-hidrogen. In the case of quantum statistical a theory based on method of moments of Grad and on the Uehling-Uhlenbeck equation is developed in order to determine the algebraic expressions to the transport coefficients. This theory is based on 13 moments of density, velocity, pressure tensor and heat flux. From the knowledge of the distribution function the constitutive equations are determinate and the transport coefficients follow from an iterative method akin to the 11axwellian procedure.

Uma nova metodologia para a medida absoluta da fração efetiva de nêutrons atrasados βeff, baseada em técnicas de análise de ruído microscópico e no modelo de Duas- Regiões, foi desenvolvida no reator IPEN/MB-01. Diferentemente das demais técnicas, tais como o Método de Bennet Modificado, o Método do Número de Nelson e o Método da fonte de 252Cf, a principal vantagem da metodologia proposta é a obtenção de βeff de um modo puramente experimental, sem a necessidade de quaisquer outros parâmetros, sejam estes calculados ou provenientes de outros experimentos. Com a finalidade de validar este novo método, uma série de experimentos Rossi-α e Feynman-α foram realizados no reator IPEN/MB-01. De acordo com a metodologia proposta, βeff foi estimado com uma incerteza de 0.67%, a qual atende aos requisitos de precisão almejados. Além disso, o tempo de geração de nêutrons prontos , dentre outros parâmetros, também foi obtido experimentalmente via esta metodologia. Em geral, os parâmetros medidos estão em acordo com resultados provenientes de experimentos de análise de ruído macroscópico. Nas comparações teoria-experimento, os valores de βeff medidos neste trabalho mostram que a biblioteca JENDL3.3 apresenta a melhor performance (dentro de 1%). Esta concordância justifica a redução no yield de fissão do 235U proposta por Sakurai e Okajima. / A new method for absolute measurement of the effective delayed neutron fraction, βeff , based on microscopic noise experiments and the Two-Region Model was developed at the IPEN/MB-01 Research Reactor facility. In contrast with other techniques like the Modified Bennet Method, Nelson-Number Method and 252Cf-Source Method, the main advantage of this new methodology is to obtain the effective delayed neutron parameters in a purely experimental way, eliminating all parameters that are difficult to measure or calculate. In this way, Rossi-α and Feynman-α experiments for validation of this method were performed at the IPEN/MB-01 facility, and adopting the present approach, βeff was measured with a 0.67% uncertainty. In addition, the prompt neutron generation time, , and other parameters were also obtained in an absolute experimental way. In general, the final results agree well with values from frequency analysis experiments. The theory-experiment comparison reveals that JENDL-3.3 shows deviation for βeff lower than 1% which meets the desired accuracy for the theoretical determination of this parameter. This work supports the reduction of the 235U thermal yield as proposed by Okajima and Sakurai.