Thesis advisor: Jeffrey Pontiff / The first essay of this dissertation studies the effect of Exchange Traded Funds (ETFs) on the yields and liquidity of the underlying corporate bonds. I find that ETFs lower the yield, have an insignificant or negative impact on the liquidity, and decrease the retail volume of constituent bonds. Overall, these results support theoretical predications that basket securities entice liquidity traders to exit the underlying market. The second essay analyzes the role of ETFs in mutual fund families and is joint work with Harold Spilker. We study mutual fund and ETF twins - index funds from the same family that follow the same benchmark. Mutual fund twins are shown to have lower tax burdens, long-term capital gains yields, and unrealized capital gains. Conversely, ETF twins have higher long-term yields and unrealized capital gains, but are compensated with lower expense ratios. Fund families benefit because twin offerings generate higher flows than their non-twin peers. These results support previous research that mutual fund families use diversification and subsidization to benefit the overall family. The third essay provides academics with a detailed understanding of the history, structure, regulation, and prospects of ETFs. The essay documents that the growth of index investing can largely be attributed to ETFs. The information and nuances discussed provide a baseline for developing future research questions and data. / Thesis (PhD) — Boston College, 2015. / Submitted to: Boston College. Carroll School of Management. / Discipline: Finance.

Here we describe the fitting and testing, via molecular dynamics simulation, of a bond-order potential for water with a unique force field parameterization. Most potentials for water, including some bond-order (reactive) potentials, are based on a traditional, many-body decomposition to describe water's structure with bond stretch, angle bend, electrostatics, and non-bonded terms. Our model uses an expanded version of the Bond Valence Model, the Valence Multipole Model, to describe all aspects of molecular structure using multibody, bond-order terms. Prior work successfully related these multibody, bond order terms to energy, provided the structures were close to equilibrium. The success of this equilibrium energy model demonstrated the plausibility of adapting its parameterization to a molecular dynamics force field. Further, we present extensive testing of ab initio methods to show that the ab initio data we obtained, using the CCSD(t)/cc-pwCVTZ level of theory, to augment the fitting set of our parameters is of the highest quality currently available for the OH system. While the force field is not yet finished, the model has demonstrated remarkable improvement since its initial testing. The test results and the insights gleaned from them have brought us significantly closer to adapting our unique parametrization to a fully functional molecular dynamics force field. Once the water potential is finished, it is our intent to develop and expand the Valence Multipole Model into a fully reactive alternative to CLAYFF, a non-reactive potential typically used to simulate fluid interfaces with clays and other minerals.

Un très grand nombre de représentations a été proposé pour modéliser la liaison chimique, mais les structures de Lewis en particulier sont largement utilisées par la communauté des chimistes expérimentateurs. Les méthodes théoriques se développant sur des structures chimiques claires de type Lewis sont essentiellement utilisées pour la description des états fondamentaux. Par ailleurs, la majorité des chimistes théoriciens utilise des orbitales moléculaires pour décrire les état excités, et manque ainsi de lisibilité. Les états excités sont difficiles à prédire, il convient donc d’utiliser un langage simple pour aboutir à une compréhension commune de ces états. Nous proposons dans cette thèse deux méthodes afin d'accéder aux états excités décrits sur des structures facilement lisibles. D’abord, une méthode de projection permettant de développer un état excité en structure chimique claire de type VB. Cette méthode est rapide car elle ne diagonalise pas d’Hamiltonien VB et elle calcule un taux de confiance servant de garde-fou pour juger la fiabilité de la description de l’état excité. Ensuite, une méthode itérative utilisant un Hamiltonien Super-IC optimise des orbitales VB pour un état excité. Cette méthode couplée à la méthode de projection ouvre un passage vers une compréhension simple des états excités. / A large number of chemical representations has been proposed to model the chemical bond, but in particular Lewis structures are widely used by the experimenters community. The theoretical methods on developing the clear chemical Lewis structures are mainly used for the description of the ground states. Moreover, the majority of theoretical chemists uses molecular orbitals to describe the excited states, and thus lacks clarity. The excited states are difficult to predict, it is appropriate to use simple language to reach a common understanding of these states. We propose in this thesis two methods to access the excited states described on easily readable structures. First, a projection method developing an excited state in clear chemical structure type VB. This method is fast because it does not VB Hamiltonian diagonalizes and calculates a trust factor for a safeguard to judge the description of the excited state. Then an iterative method using a Super-CI Hamiltonian to optimize VB orbitals to an excited state. This method coupled with the projection method opens a way to a simple understanding of the excited states.

The research provided in this report examines the behavior of fiber reinforced polymer (FRP) reinforcing bars, embedded in normal weight concrete (NWC) hinged beam-end specimens, tested in accordance with two laboratory conditions. Reinforcing bars of different diameter, material configuration, and finished surface preparation were tested for bond strength parameters determined in accordance with ACI Committee Report 440.3. Bond strength parameters under the first condition were tested within NWC beams at a relatively low compressive strength and minimum embedment length; the second condition allowed testing within NWC beams at twice the design compressive strength of the first condition and moderate embedment length. The load-slip curves developed show the differences that occur under the specified conditions. The influence of embedment length, bar diameter, material configuration, finished surface preparation, and concrete compressive strength are reported in detail. Furthermore, the testing arrangement selected for this study was proven to have a significant influence on bond behavior when compared to conventional pullout test methods.

This dissertation is mainly focused on charge assisted noncovalent interactions specially hydrogen and halogen bonds. Generally, noncovalent interactions are only weak forces of interaction but an introduction of suitable charge on binding units increases the strength of the noncovalent bonds by a several orders of magnitude. These charge assisted noncovalent interactions have wide ranges of applications from crystal engineering to drug design. Not only that, nature accomplishes a number of important tasks using these interactions. Although, a good number of theoretical and experimental studies have already been done in this field, some fundamental properties of charge assisted hydrogen and halogen bonds still lack molecular level understanding and their electronic properties are yet to be explored. Better understanding of the electronic properties of these bonds will have applications on the rational design of drugs, noble functional materials, catalysts and so on. In most of this dissertation, comparative studies have been made between charge and neutral noncovalent interactions by quantum mechanical calculations. The comparisons are primarily focused on energetics and the electronic properties. In most of the cases, comparative studies are also made between hydrogen and halogen bonds which contradict the long time notion that the H-bond is the strongest noncovalent interactions.Besides that, this dissertation also explores the long range behavior and directional properties of various neutral and charge assisted noncovalent bonds.

Bond in a reinforced concrete (RC) structure is the interaction force that transfers force between the steel and concrete. It influences the structural performance and serviceability of a structure under both static and cyclic loading. Corrosion of reinforcing steel in RC structures is the primary reason behind bond loss in RC elements. A loss of bond in concrete results in a decrease in the serviceability strength and eventually causes a brittle and sudden failure. Structures, such as bridges, are vulnerable to corrosion and at the same time are subjected to repeated loading rather than static loading. Nevertheless, little experimental or analytical studies that address the problem of corroded steel-concrete bond under repeated loading exist. This study was aimed at increasing the understanding of the behaviour of bond between corroded reinforcing steel bars and concrete for structures subjected to repeated loading. In addition, the effect of fibre reinforced polymers (FRP) as a rehabilitation method was assessed. Fibre reinforced polymers is considered to be a state-of-the art rehabilitation material due to its advantages, such as high strength, light weight and ease of handling and application. Forty-seven anchorage-beam specimens were cast and tested. The specimens’ dimensions were 152 x 254 x 2000 mm reinforced with two 20M bars. The steel reinforcement in a specimen was unbonded except for 250 mm from each end. This bonded length was selected to ensure a bond failure. The corrosion was induced using an accelerated corrosion process. The parameters investigated were the corrosion level (0, 5 and 9% measured mass loss), whether the specimen was wrapped in the anchorage zone with a U-shaped carbon fibre reinforced polymer (CFRP) sheets or not, and the load range applied. The minimum load applied was 10% of the static bond capacity of the specimen. The maximum load was varied to give the desired range of fatigue lives (103 to 106 cycles). The test frequency for all repeated tests was 1.5 Hz. Results showed that the repeated loading either pushed the bottom concrete cover away from the steel bar by wedge action for unwrapped beams or cracked and crushed the CFRP confined bottom concrete cover for wrapped beams. The concrete damage caused the bond stress to undergo a gradual redistribution, moving the peak bond stress from the loaded end towards the free end, resulting in failure of the specimens by fatigue of bond. Corrosion levels of 5% and 9% decreased the fatigue bond strength on average by 19%. The rate of slip of the steel bar increased as the corrosion level increased. CFRP sheets changed the mechanism by which the concrete resist the bond forces by engaging the bottom cover. This in turn increased the fatigue bond strength at all corrosion levels on average by 31% compared to unwrapped specimens. Based on the test results and observations, a hypothesis of the mechanics of bond under repeated loading was postulated and a fatigue slip-growth analysis (similar to the fracture mechanics crack growth approach) was proposed to calculate the fatigue life of a specimen that fail in bond. The proposed analysis was in reasonable agreement with the experimental results.

This thesis demonstrates the feasibility of methods developed to increase the quality of the crescent bond together with the tail bond quality. Low pull force of the crescent bond limits the usage of insulated Au wire in microelectronics assembly. Premature break of the tail which results in the stoppage of the bonding machine is one of obstacles to overcome for Cu wire. The primary focus of this thesis is to understand the tail and crescent bonding process and then to propose methodologies to improve thermosonic wire bonding processes when Cu and insulated Au wires are used. Several series of experiments to investigate the crescent and tail bonding processes are performed on auto bonders. Cu and insulated Au wires with diameters of 25mm are bonded on the diepads of Ag leadframes. For simplicity, wire loops are oriented perpendicular to the ultrasonic direction. It was found that the crescent bond breaking force by pulling the wire loop (pull force) with insulated Au wire is about 80 % of that of bare Au wire. A modification of the crescent bonding process is made to increase the pull force with insulated Au wire. In the modified process, an insulation layer removing stage (cleaning stage) is inserted before the bonding stage. The cleaning stage consists of a scratching motion (shift) toward to the ball bond in combination with ultrasound. Bonds are then made on the fresh diepad with the insulation removed from the contact surface of the insulated Au wire. This process increases the pull force of the crescent bond up to 26% which makes it comparable to the results obtained with bare Au wire. An online tail breaking force measurement method is developed with a proximity sensor between wire clamp and horn. Detailed understanding of tail bond formation is achieved by studying tail bond imprints with scanning electron microscopy and energy dispersive x-ray analysis. Descriptions are given of the dependence of the tail breaking force on the bonding parameters, metallization variation, and cleanliness of the bond pad. Simultaneous optimization with pull force and tail breaking force can optimize the Cu wire bonding process both with high quality and robustness. It is recommended to first carry out conventional pull force optimization followed by a minimization of the bonding force parameter to the lowest value still fulfilling the pull force cpk requirement. The tail bond forms not only under the capillary chamfer, but also under the capillary hole. The tail breaking force includes both the interfacial bond breaking strength and the breaking strength of the thinned portion of the wire that will remain at the substrate as residue. Close investigations of the tail bond imprint with scanning electron microscopy indicate the presence of fractures of the substrate indicating substrate material being picked up by Cu wire tail. Pick up is found on Au and Cu wires, but the amount of pick up is much larger on Cu wire. The effect on the hardness of the subsequently formed Cu free air ball (FAB) as investigated with scanning electron microscopy and micro - hardness test shows that Cu FABs containing Au and Ag pick ups are softer than those without pick up. However, the hardness varies significantly more with Au pick up. The amount of Au pick up is estimated higher than 0.03 % of the subsequently formed FAB volume, exceeding typical impurity and dopant concentrations (0.01 %) added during manufacturing of the wire.

Bond in a reinforced concrete (RC) structure is the interaction force that transfers force between the steel and concrete. It influences the structural performance and serviceability of a structure under both static and cyclic loading. Corrosion of reinforcing steel in RC structures is the primary reason behind bond loss in RC elements. A loss of bond in concrete results in a decrease in the serviceability strength and eventually causes a brittle and sudden failure. Structures, such as bridges, are vulnerable to corrosion and at the same time are subjected to repeated loading rather than static loading. Nevertheless, little experimental or analytical studies that address the problem of corroded steel-concrete bond under repeated loading exist. This study was aimed at increasing the understanding of the behaviour of bond between corroded reinforcing steel bars and concrete for structures subjected to repeated loading. In addition, the effect of fibre reinforced polymers (FRP) as a rehabilitation method was assessed. Fibre reinforced polymers is considered to be a state-of-the art rehabilitation material due to its advantages, such as high strength, light weight and ease of handling and application. Forty-seven anchorage-beam specimens were cast and tested. The specimens’ dimensions were 152 x 254 x 2000 mm reinforced with two 20M bars. The steel reinforcement in a specimen was unbonded except for 250 mm from each end. This bonded length was selected to ensure a bond failure. The corrosion was induced using an accelerated corrosion process. The parameters investigated were the corrosion level (0, 5 and 9% measured mass loss), whether the specimen was wrapped in the anchorage zone with a U-shaped carbon fibre reinforced polymer (CFRP) sheets or not, and the load range applied. The minimum load applied was 10% of the static bond capacity of the specimen. The maximum load was varied to give the desired range of fatigue lives (103 to 106 cycles). The test frequency for all repeated tests was 1.5 Hz. Results showed that the repeated loading either pushed the bottom concrete cover away from the steel bar by wedge action for unwrapped beams or cracked and crushed the CFRP confined bottom concrete cover for wrapped beams. The concrete damage caused the bond stress to undergo a gradual redistribution, moving the peak bond stress from the loaded end towards the free end, resulting in failure of the specimens by fatigue of bond. Corrosion levels of 5% and 9% decreased the fatigue bond strength on average by 19%. The rate of slip of the steel bar increased as the corrosion level increased. CFRP sheets changed the mechanism by which the concrete resist the bond forces by engaging the bottom cover. This in turn increased the fatigue bond strength at all corrosion levels on average by 31% compared to unwrapped specimens. Based on the test results and observations, a hypothesis of the mechanics of bond under repeated loading was postulated and a fatigue slip-growth analysis (similar to the fracture mechanics crack growth approach) was proposed to calculate the fatigue life of a specimen that fail in bond. The proposed analysis was in reasonable agreement with the experimental results.

This thesis demonstrates the feasibility of methods developed to increase the quality of the crescent bond together with the tail bond quality. Low pull force of the crescent bond limits the usage of insulated Au wire in microelectronics assembly. Premature break of the tail which results in the stoppage of the bonding machine is one of obstacles to overcome for Cu wire. The primary focus of this thesis is to understand the tail and crescent bonding process and then to propose methodologies to improve thermosonic wire bonding processes when Cu and insulated Au wires are used. Several series of experiments to investigate the crescent and tail bonding processes are performed on auto bonders. Cu and insulated Au wires with diameters of 25mm are bonded on the diepads of Ag leadframes. For simplicity, wire loops are oriented perpendicular to the ultrasonic direction. It was found that the crescent bond breaking force by pulling the wire loop (pull force) with insulated Au wire is about 80 % of that of bare Au wire. A modification of the crescent bonding process is made to increase the pull force with insulated Au wire. In the modified process, an insulation layer removing stage (cleaning stage) is inserted before the bonding stage. The cleaning stage consists of a scratching motion (shift) toward to the ball bond in combination with ultrasound. Bonds are then made on the fresh diepad with the insulation removed from the contact surface of the insulated Au wire. This process increases the pull force of the crescent bond up to 26% which makes it comparable to the results obtained with bare Au wire. An online tail breaking force measurement method is developed with a proximity sensor between wire clamp and horn. Detailed understanding of tail bond formation is achieved by studying tail bond imprints with scanning electron microscopy and energy dispersive x-ray analysis. Descriptions are given of the dependence of the tail breaking force on the bonding parameters, metallization variation, and cleanliness of the bond pad. Simultaneous optimization with pull force and tail breaking force can optimize the Cu wire bonding process both with high quality and robustness. It is recommended to first carry out conventional pull force optimization followed by a minimization of the bonding force parameter to the lowest value still fulfilling the pull force cpk requirement. The tail bond forms not only under the capillary chamfer, but also under the capillary hole. The tail breaking force includes both the interfacial bond breaking strength and the breaking strength of the thinned portion of the wire that will remain at the substrate as residue. Close investigations of the tail bond imprint with scanning electron microscopy indicate the presence of fractures of the substrate indicating substrate material being picked up by Cu wire tail. Pick up is found on Au and Cu wires, but the amount of pick up is much larger on Cu wire. The effect on the hardness of the subsequently formed Cu free air ball (FAB) as investigated with scanning electron microscopy and micro - hardness test shows that Cu FABs containing Au and Ag pick ups are softer than those without pick up. However, the hardness varies significantly more with Au pick up. The amount of Au pick up is estimated higher than 0.03 % of the subsequently formed FAB volume, exceeding typical impurity and dopant concentrations (0.01 %) added during manufacturing of the wire.

N-phenylpyridin-2-amine , treated with stochiometric amount of palladium(II) acetate in dichloromethane at 65-70¢J for 4 h, to give high yield palladacycle 53. The reaction of palladacycle 53 with potassium aryltrifluoroborates in 1,4-dioxane at 140¢J for 24 h, could give a variety of N-(2-pyridinyl)carbazoles 55a-55m via sequential C-H bond activation. Carbazole derivative 55a reacted with irdium chloride gave iridium dimer, which followed by addition of picolinic acid via ligand exchange will form iridium complexes, which can further be utilized as OLEDs materials.