Ab Initio Quantum Chemical Studies on Neutral-Radical Reactions of Ethynyl (C2H) and Cyano (CN) with Unsaturated Hydrocarbons

An Ab Initio/RRKM study of the reaction mechanism and product branching ratios of neutral-radical ethynyl (C2H) and cyano (CN) radical species with unsaturated hydrocarbons is performed. The reactions studied apply to cold conditions such as planetary atmospheres including Titan, the Interstellar Medium (ISM), icy bodies and molecular clouds. The reactions of C2H and CN additions to gaseous unsaturated hydrocarbons are an active area of study. NASA’s Cassini/Huygens mission found a high concentration of C2H and CN from photolysis of ethyne (C2H2) and hydrogen cyanide (HCN), respectively, in the organic haze layers of the atmosphere of Titan. The reactions involved in the atmospheric chemistry of Titan lead to a vast array of larger, more complex intermediates and products and may also serve as a chemical model of Earth’s primordial atmospheric conditions. The C2H and CN additions are rapid and exothermic, and often occur barrierlessly to various carbon sites of unsaturated hydrocarbons. The reaction mechanism is proposed on the basis of the resulting potential energy surface (PES) that includes all the possible intermediates and transition states that can occur, and all the products that lie on the surface. The B3LYP/6-311g(d,p) level of theory is employed to determine optimized electronic structures, moments of inertia, vibrational frequencies, and zero-point energy. They are followed by single point higher-level CCSD(T)/cc-vtz calculations, including extrapolations to complete basis sets (CBS) of the reactants and products. A microcanonical RRKM study predicts single-collision (zero-pressure limit) rate constants of all reaction paths on the potential energy surface, which is then used to compute the branching ratios of the products that result. These theoretical calculations are conducted either jointly or in parallel to experimental work to elucidate the chemical composition of Titan’s atmosphere, the ISM, and cold celestial bodies.

Alchemy and Symbolism in the Work of Carlos Estevez

The purpose of this thesis was to explore how alchemy has influenced Carlos Estevez’s work through a study of the symbolic repertoire and the philosophical concepts associated with it in his art, particularly how these are expressed in his artworks and how alchemy has evolved thematically in his oeuvre. The study of alchemy influenced this artist so deeply that even pieces that were not primarily inspired by this philosophical system show traces of it, essentially by representing the concept of transformation, crucial to understanding the alchemical process. This thesis is based on Carl Gustav Jung’s idea of metaphysical transformation as one of the main aspects of alchemy, and on his theory of active imagination as a tool to represent thoughts through artworks. Alchemy transformed Estevez’s art, and by extension the way he approaches life, making him conscious of the importance of transmutation and alchemical concepts.

Host and Network Optimizations for Performance Enhancement and Energy Efficiency in Data Center Networks

Modern data centers host hundreds of thousands of servers to achieve economies of scale. Such a huge number of servers create challenges for the data center network (DCN) to provide proportionally large bandwidth. In addition, the deployment of virtual machines (VMs) in data centers raises the requirements for efficient resource allocation and find-grained resource sharing. Further, the large number of servers and switches in the data center consume significant amounts of energy. Even though servers become more energy efficient with various energy saving techniques, DCN still accounts for 20% to 50% of the energy consumed by the entire data center. The objective of this dissertation is to enhance DCN performance as well as its energy efficiency by conducting optimizations on both host and network sides. First, as the DCN demands huge bisection bandwidth to interconnect all the servers, we propose a parallel packet switch (PPS) architecture that directly processes variable length packets without segmentation-and-reassembly (SAR). The proposed PPS achieves large bandwidth by combining switching capacities of multiple fabrics, and it further improves the switch throughput by avoiding padding bits in SAR. Second, since certain resource demands of the VM are bursty and demonstrate stochastic nature, to satisfy both deterministic and stochastic demands in VM placement, we propose the Max-Min Multidimensional Stochastic Bin Packing (M3SBP) algorithm. M3SBP calculates an equivalent deterministic value for the stochastic demands, and maximizes the minimum resource utilization ratio of each server. Third, to provide necessary traffic isolation for VMs that share the same physical network adapter, we propose the Flow-level Bandwidth Provisioning (FBP) algorithm. By reducing the flow scheduling problem to multiple stages of packet queuing problems, FBP guarantees the provisioned bandwidth and delay performance for each flow. Finally, while DCNs are typically provisioned with full bisection bandwidth, DCN traffic demonstrates fluctuating patterns, we propose a joint host-network optimization scheme to enhance the energy efficiency of DCNs during off-peak traffic hours. The proposed scheme utilizes a unified representation method that converts the VM placement problem to a routing problem and employs depth-first and best-fit search to find efficient paths for flows.

Silicon Photonic Device for Wavelength Sensing and Monitoring

Over the last decade advances and innovations from Silicon Photonics technology were observed in the telecommunications and computing industries. This technology which employs Silicon as an optical medium, relies on current CMOS micro-electronics fabrication processes to enable medium scale integration of many nano-photonic devices to produce photonic integrated circuitry. However, other fields of research such as optical sensor processing can benefit from silicon photonics technology, specially in sensors where the physical measurement is wavelength encoded. In this research work, we present a design and application of a thermally tuned silicon photonic device as an optical sensor interrogator. The main device is a micro-ring resonator filter of 10 $\mu m$ of diameter. A photonic design toolkit was developed based on open source software from the research community. With those tools it was possible to estimate the resonance and spectral characteristics of the filter. From the obtained design parameters, a 7.8 x 3.8 mm optical chip was fabricated using standard micro-photonics techniques. In order to tune a ring resonance, Nichrome micro-heaters were fabricated on top of the device. Some fabricated devices were systematically characterized and their tuning response were determined. From measurements, a ring resonator with a free-spectral-range of 18.4 nm and with a bandwidth of 0.14 nm was obtained. Using just 5 mA it was possible to tune the device resonance up to 3 nm. In order to apply our device as a sensor interrogator in this research, a model of wavelength estimation using time interval between peaks measurement technique was developed and simulations were carried out to assess its performance. To test the technique, an experiment using a Fiber Bragg grating optical sensor was set, and estimations of the wavelength shift of this sensor due to axial strains yield an error within 22 pm compared to measurements from spectrum analyzer. Results from this study implies that signals from FBG sensors can be processed with good accuracy using a micro-ring device with the advantage of ts compact size, scalability and versatility. Additionally, the system also has additional applications such as processing optical wavelength shifts from integrated photonic sensors and to be able to track resonances from laser sources.

Time Orientation in Organizations: Polychronicity and Multitasking

This dissertation consists of four studies examining two constructs related to time orientation in organizations: polychronicity and multitasking. The first study investigates the internal structure of polychronicity and its external correlates in a sample of undergraduate students (N = 732). Results converge to support a one-factor model and finds measures of polychronicity to be significantly related to extraversion, agreeableness, and openness to experience. The second study quantitatively reviews the existing research examining the relationship between polychronicity and the Big Five factors of personality. Results reveal a significant relationship between extraversion and openness to experience across studies. Studies three and four examine the usefulness of multitasking ability in the prediction of work related criteria using two organizational samples (N = 175 and 119, respectively). Multitasking ability demonstrated predictive validity, however the incremental validity over that of traditional predictors (i.e., cognitive ability and the Big Five factors of personality) was minimal. The relationships between multitasking ability, polychronicity, and other individual differences were also investigated. Polychronicity and multitasking ability proved to be distinct constructs demonstrating differential relationships with cognitive ability, personality, and performance. Results provided support for multitasking performance as a mediator in the relationship between multitasking ability and overall job performance. Additionally, polychronicity moderated the relationship between multitasking ability and both ratings of multitasking performance and overall job performance in Study four. Clarification of the factor structure of polychronicity and its correlates will facilitate future research in the time orientation literature. Results from two organizational samples point to work related measures of multitasking ability as a worthwhile tool for predicting the performance of job applicants.

Historiographic Metafiction and the Neo-slave Narrative: Pastiche and Polyphony in Caryl Phillips, Toni Morrison and Sherley Anne Williams

The classic slave narrative recounted a fugitive slave’s personal story condemning slavery and hence working towards abolition. The neo-slave narrative underlines the slave’s historical legacy by unveiling the past through foregrounding African Atlantic experiences in an attempt to create a critical historiography of the Black Atlantic. The neo-slave narrative is a genre that emerged following World War II and presents us with a dialogue combining the history of 1970 - 2000. In this thesis I seek to explore how the contemporary counter-part of the classic slave narrative draws, reflects or diverges from the general conventions of its predecessor. I argue that by scrutinizing our notion of truth, the neo-slave narrative remains a relevant, important witness to the history of slavery as well as to today’s still racialized society. The historiographic metafiction of the neo-slave narrative rewrites history with the goal of digesting the past and ultimately leading to future reconciliation.

A Longitudinal Exploration of the Relationship Between Oral Reading Fluency and Reading Comprehension Achievement Among a Sample of Diverse Young Learners

Exploring the relationship between early oral reading fluency ability and reading comprehension achievement among an ethnically and racially diverse sample of young learners from low-income families, attending elementary school within a large public school district in southeast Florida is the purpose of this longitudinal study. Although many studies have been conducted to address the relationship between oral reading fluency ability and reading comprehension achievement, most of the existing research failed either to disaggregate the data by demographic subgroups or secure a large enough sample of students to adequately represent the diverse subgroups. The research questions that guided this study were: (a) To what extent does early oral reading fluency ability measured in first, second, or third grade correlate with reading comprehension achievement in third grade? (b) To what extent does the relationship of early oral reading fluency ability and reading comprehension achievement vary by demographic subgroup membership (i.e., gender, race/ethnicity, socioeconomic status) among a diverse sample of students? A predictive research design using archived secondary data was employed in this nonexperimental quantitative methods study of 1,663 third grade students who attended a cohort of 25 Reading First funded schools. The data analyzed derived from the Dynamic Indicators of Basic Early Literacy Skills Oral Reading Fluency (DIBELS ORF) measure administered in first, second, and third grades and the Florida Comprehensive Assessment Test of the Sunshine State Standards (FCAT-SSS) Reading administered in third grade. Linear regression analyses between each of the oral reading fluency and reading comprehension measures produced significant positive correlations. Hierarchical regression analyses supported the predictive potential of all three oral reading fluency ability measures toward reading comprehension achievement, with the first grade oral reading fluency ability measure explaining the most significant variance in third grade reading comprehension achievement. Male students produced significant overall differences in variance when compared to female students as did the Other student subgroup (i.e., Asian, Multiracial, and Native American) when compared to Black, White, and Hispanic students. No significant differences in variance were produced between students from low and moderate socioeconomic families. These findings are vital toward adding to the literature of diverse young learners.

Developing an Enhanced Model for Combined Heat and Air Infiltration Energy Simulation

The need for efficient, sustainable, and planned utilization of resources is ever more critical. In the U.S. alone, buildings consume 34.8 Quadrillion (1015) BTU of energy annually at a cost of $1.4 Trillion. Of this energy 58% is utilized for heating and air conditioning. Several building energy analysis tools have been developed to assess energy demands and lifecycle energy costs in buildings. Such analyses are also essential for an efficient HVAC design that overcomes the pitfalls of an under/over-designed system. DOE-2 is among the most widely known full building energy analysis models. It also constitutes the simulation engine of other prominent software such as eQUEST, EnergyPro, PowerDOE. Therefore, it is essential that DOE-2 energy simulations be characterized by high accuracy. Infiltration is an uncontrolled process through which outside air leaks into a building. Studies have estimated infiltration to account for up to 50% of a building’s energy demand. This, considered alongside the annual cost of buildings energy consumption, reveals the costs of air infiltration. It also stresses the need that prominent building energy simulation engines accurately account for its impact. In this research the relative accuracy of current air infiltration calculation methods is evaluated against an intricate Multiphysics Hygrothermal CFD building envelope analysis. The full-scale CFD analysis is based on a meticulous representation of cracking in building envelopes and on real-life conditions. The research found that even the most advanced current infiltration methods, including in DOE-2, are at up to 96.13% relative error versus CFD analysis. An Enhanced Model for Combined Heat and Air Infiltration Simulation was developed. The model resulted in 91.6% improvement in relative accuracy over current models. It reduces error versus CFD analysis to less than 4.5% while requiring less than 1% of the time required for such a complex hygrothermal analysis. The algorithm used in our model was demonstrated to be easy to integrate into DOE-2 and other engines as a standalone method for evaluating infiltration heat loads. This will vastly increase the accuracy of such simulation engines while maintaining their speed and ease of use characteristics that make them very widely used in building design.

Centered Fluidity and the Horizons of Continuity in Djuna Barnes' Nightwood

Modern writers like Djuna Barnes allow for the post-modern fluidity and explosion of sex and gender without finalizing either in a fixed form. Whereas the classical, archetypal androgyne is made up of two halves, one man and one woman; the deconstructed androgynous figure is not constituted of oppositional terms which would reflect an essential and unimpeachable truth. I reveal the way Djuna Barnes’ Nightwood not only thematizes the fluid androgyne, but also cleverly verbalizes David Wood’s perpetual and un-dischargable “debt” to extra-discursivity while poetically critiquing gender “appropriateness,” societal constraints, and the constitution of identity. Barnes presents a decentralized, ungrounded and non-prescribed world in Nightwood not only through her cross-dressing and androgynous characters, but also in her poetics, her assertion of the open-ended quality of language, and a strong imperative to negotiate our physical existence in a world of fluid gender and sexual boundaries.

Risk Factors and Associations for Hepatitis C Infection among Hispanic/Latino Intravenous Drug Users in Miami-Dade County, Florida

Hepatitis C infection (HCV) continues to disproportionately affect Hispanics/Latinos in the United States. Hispanic/Latino intravenous drug users (IDUs), because of their risky injection and sexual behaviors, are prone to HCV infection and rapid transmission of the virus to others via several routes. With a prevalence rate of approximately 75% among IDUs, it is imperative that transmission of HCV be prevented in this population. This study aims to examine the associations between demographic, injection and sexual risk factors to HCV infection in a group Hispanic/Latino IDUs in Miami-Dade County, Florida. Preliminary unadjusted results in this sample reveal that age (OR=4.592, p=0.004), weekly injection (OR=5.171, p=0.000), daily injection frequency (OR=3.856, p=0.000) and use of a dirty needle (OR=2.320, p= 0.006) were all significantly associated with HCV infection. Being born outside the U.S. was significantly negatively associated with HCV infection (OR=0.349, p=0.004). Additionally, having two or more sex partners in the past three months (OR=0.472, p=0.014) was negatively associated with HCV infection. After adjusting for all other variables, older age (AOR=7.470, p=0.006), weekly injection (AOR=3.238, p=0.007) and daily injection frequency (AOR=2.625, p=0.010) were all significantly associated with HCV infection. Being born outside the U.S. (AOR=0.369, p=0.019) was a significant protective factor for HCV infection, along with having two or more sex partners in the past three months (AOR=0.481, p=0.037). When analyzing the significant variables in a backward regression model, having 2 or more sex partners in the past three months was not significant at the p

The Impact of Friends on Newly Immigrant Children’s Emotional and Behavioral Adjustment

Immigration disrupts an individual’s support network; however, the stresses of the immigration process increase the need for social support. The presence of social support becomes essential for immigrant children and adolescents to cope with these important transitional circumstances. Friends are both sources of social support and models for behavior. Furthermore, friendship networks are known to have a significant influence on youths’ functioning. Literature suggests that peer relations become more important in adolescence and friend support is related to child and adolescent well-being. Thus, friend relationships may be particularly important for immigrant youths who experience disruption in their friendship networks during the process of migration to another country. In addition to friendship networks and support, friend characteristics also need to be taken into consideration as important factors for immigrant youth adjustment. My study involved analyses of the effects of friend support and friend problem behaviors on emotional and behavioral functioning for elementary, middle, and high school age newly immigrant children and adolescents. Immigrant children and adolescents (N = 503) were interviewed at schools by interviewers fluent in participants’ languages. Structural Equation Modeling (SEM) analyses revealed that friend support and friend problem behaviors were related to children’s self-esteem and externalizing behaviors. In addition, friend problem behavior alone predicted children’s psychological symptoms and depression scores. Furthermore, age/grade was found to be a moderator for the relation between friend problem behavior and immigrant youth behavioral adjustment such that compared to elementary and high school cohorts, middle school youths showed more externalizing behaviors when they had friends performing problem behaviors. Results supported the idea that both friend support and friend behavior are related to newly immigrant youths’ emotional and behavioral adjustment. This study informs further research and interventions concerning the development of programs to facilitate immigrant youths’ adjustment by revealing friendship factors related to their adaptation.

Organized Labor and U.S. Foreign Policy: The Solidarity Center in Historical Context

During the Cold War the foreign policy of the American Federation of Labor and Congress of Industrial Organizations (AFL-CIO), was heavily criticized by scholars and activists for following the lead of the U.S. state in its overseas operations. In a wide range of states, the AFL-CIO worked to destabilize governments selected by the U.S. state for regime change, while in others the Federation helped stabilize client regimes of the U.S. state. In 1997 the four regional organizations that previously carried out AFL-CIO foreign policy were consolidated into the American Center for International Labor Solidarity (Solidarity Center). My dissertation is an attempt to analyze whether the foreign policy of the AFL-CIO in the Solidarity Center era is marked by continuity or change with past practices. At the same time, this study will attempt to add to the debate over the role of non-governmental organizations (NGOs) in the post-Cold War era, and its implications for future study. Using the qualitative “process-tracing” detailed by of Alexander George and Andrew Bennett (2005) my study examines a wide array of primary and secondary sources, including documents from the NED and AFL-CIO, in order to analyze the relationship between the Solidarity Center and the U.S. state from 2002-2009. Furthermore, after analyzing broad trends of NED grants to the Solidarity Center, this study examines three dissimilar case studies including Venezuela, Haiti, and Iraq and the Middle East and North African (MENA) region to further explore the connections between U.S. foreign policy goals and the Solidarity Center operations. The study concludes that the evidence indicates continuity with past AFL-CIO foreign policy practices whereby the Solidarity Center follows the lead of the U.S. state. It has been found that the patterns of NED funding indicate that the Solidarity Center closely tailors its operations abroad in areas of importance to the U.S. state, that it is heavily reliant on state funding via the NED for its operations, and that the Solidarity Center works closely with U.S. allies and coalitions in these regions. Finally, this study argues for the relevance of “top-down” NGO creation and direction in the post-Cold War era.

Evaluation of the Evidential Value of the Elemental Composition of Glass, Ink and Paper by Laser-Based Micro-Spectrochemical Methods

Elemental analysis can become an important piece of evidence to assist the solution of a case. The work presented in this dissertation aims to evaluate the evidential value of the elemental composition of three particular matrices: ink, paper and glass. In the first part of this study, the analytical performance of LIBS and LA-ICP-MS methods was evaluated for paper, writing inks and printing inks. A total of 350 ink specimens were examined including black and blue gel inks, ballpoint inks, inkjets and toners originating from several manufacturing sources and/or batches. The paper collection set consisted of over 200 paper specimens originating from 20 different paper sources produced by 10 different plants. Micro-homogeneity studies show smaller variation of elemental compositions within a single source (i.e., sheet, pen or cartridge) than the observed variation between different sources (i.e., brands, types, batches). Significant and detectable differences in the elemental profile of the inks and paper were observed between samples originating from different sources (discrimination of 87 – 100% of samples, depending on the sample set under investigation and the method applied). These results support the use of elemental analysis, using LA-ICP-MS and LIBS, for the examination of documents and provide additional discrimination to the currently used techniques in document examination. In the second part of this study, a direct comparison between four analytical methods (µ-XRF, solution-ICP-MS, LA-ICP-MS and LIBS) was conducted for glass analyses using interlaboratory studies. The data provided by 21 participants were used to assess the performance of the analytical methods in associating glass samples from the same source and differentiating different sources, as well as the use of different match criteria (confidence interval (±6s, ±5s, ±4s, ±3s, ±2s), modified confidence interval, t-test (sequential univariate, p=0.05 and p=0.01), t-test with Bonferroni correction (for multivariate comparisons), range overlap, and Hotelling’s T2 tests. Error rates (Type 1 and Type 2) are reported for the use of each of these match criteria and depend on the heterogeneity of the glass sources, the repeatability between analytical measurements, and the number of elements that were measured. The study provided recommendations for analytical performance-based parameters for µ-XRF and LA-ICP-MS as well as the best performing match criteria for both analytical techniques, which can be applied now by forensic glass examiners.

Living on Both Sides of the Fence: A Phenomenological Study of Human Resource Development Professionals as Downsizing Survivors and Strategic Human Resource Development Facilitators

This phenomenological study explored how HR professionals who identified themselves as facilitators of strategic HRD (SHRD) perceived the experience of being an organizational agent-downsizing survivor. Criterion and snowball sampling were used to recruit 15 participants for this study. A semi-structured interview guide was used to interview participants. Creswell’s (2007) simplified version of Moustakas’s (1994) Modification of the Stevick-Colaizzi-Keen Method of Analysis of Phenomenological Data was used to analyze the data. Four main themes and corresponding sub-themes emerged from an inductive data analysis. The four main themes were a) the emotionality of downsizing, b) feeling responsible, c) choice and control, and d) possibilities for growth. Participants perceived downsizing as an emotional organizational change event that required them to manage their own emotions while helping others do the same. They performed their roles within an organizational atmosphere that was perceived as chaotic and filled with apprehension, shock, and a sense of ongoing loss, sadness and grieving. They sometimes experienced guilt and doubt and felt deceptive for having to keep secrets from others when planning for downsizing. Participants felt a strong sense of responsibility to protect employees emotionally, balance employee and organizational interests, and try to ensure the best outcomes for both. Often being there for others meant that they put on their games faces and took care of themselves last. Participants spoke of the importance of choosing one’s attitude, being proactive rather than reactive, and finding ways to regain control in the midst of organizational crisis. They also perceived that although downsizing was emotionally difficult to go through that it provided possibilities for self, employee, and organizational growth.

Spatiotemporal Variation in Abundance and Social Structure of Bottlenose Dolphins in the Florida Coastal Everglades

Bottlenose dolphins (Tursiops truncatus) are large-bodied predators that are locally abundant in the coastal Everglades. Because of their potential to exert strong top-down effects on their communities, it is important to understand how spatiotemporal variation in biotic and abiotic factors affects the abundance and behavior of dolphins. This study combined two years of transect surveys with photographic identification methods to assess spatiotemporal variation in the abundance and group sizes of bottlenose dolphins across four large regions of the coastal Everglades including the Shark and Harney Rivers, Whitewater Bay, and coastal oceans of the Gulf of Mexico and Florida Bay. Dolphin abundance was similar across wet and dry seasons, except in river habitats where abundances were higher during the dry season. Group sizes were largest in Florida Bay and open water. Dolphins may be relatively resilient to abiotic changes in the coastal Everglades, with the possible exception of river habitats.