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.<.

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.

Understanding the Impact of the Property Tax Appeal Process on Assessment Uniformity: Procedures, Structures, and Outcomes

Property taxes serve as a vital revenue source for local governments. The revenues derived from the property tax function as the primary funding source for a variety of critical local public service systems. Property tax appeal systems serve as quasi-administrative-judicial mechanisms intended to assure the public that property tax assessments are correct, fair, and equitable. Despite these important functions, there is a paucity of empirical research related to property tax appeal systems. This study contributes to property tax literature by identifying who participates in the property tax appeal process and examining their motivations for participation. In addition, the study sought to determine whether patterns of use and success in appeal systems affected the distribution of the tax burden. Data were collected by means of a survey distributed to single-family property owners from two Florida counties. In addition, state and county documents were analyzed to determine appeal patterns and examine the impact on assessment uniformity, over a three-year period. The survey data provided contextual evidence that single-family property owners are not as troubled by property taxes as they are by the conduct of local government officials. The analyses of the decision to appeal indicated that more expensive properties and properties excluded from initial uniformity analyses were more likely to be appealed, while properties with homestead exemptions were less likely to be appealed. The value change analyses indicated that appeals are clustered in certain geographical areas; however, these areas do not always experience a greater percentage of the value changes. Interestingly, professional representation did not increase the probability of obtaining a reduction in value. Other relationships between the variables were discovered, but often with weak predictive ability. Findings from the assessment uniformity analyses were also interesting. The results indicated that the appeals mechanisms in both counties improved assessment uniformity. On average, appealed properties exhibited greater horizontal and vertical inequities, as compared to non-appealed properties, prior to the appeals process. After, the appeal process was completed; the indicators of horizontal and vertical equity were largely improved. However, there were some indications of regressivity in the final year of the study.

The correlation of structure and electronic properties near the surface of transition metal oxides

The strong couplings between different degrees of freedom are believed to be responsible for novel and complex phenomena discovered in transition metal oxides (TMOs). The physical complexity is directly responsible for their tunability. Creating surfaces/interfaces add an additional ' man-made' twist, approaching the quantum phenomena of correlated materials. ^ The dissertation focused on the structural and electronic properties in proximity of surface of three prototype TMO compounds by using three complementary techniques: scanning tunneling microscopy, angle-resolved photoelectron spectroscopy and low energy electron diffraction, particularly emphasized the effects of broken symmetry and imperfections like defects on the coupling between charge and lattice degrees of freedom. ^ Ca1.5Sr0.5RuO4 is a layered ruthenate with square lattice and at the boundary of magnetic/orbital instability in Ca2-xSrxRuO4. That the substitution of Sr 2+ with Ca2+ causing RuO6 rotation narrows the dxy band width and changes the Fermi surface topology. Particularly, the γ(dxy) Fermi surface sheet exhibited hole-like in Ca1.5Sr0.5RuO4 in contrast to electron-like in Sr2RuO4, showing a strong charge-lattice coupling. ^ Na0.75CoO2 is a layered cobaltite with triangular lattice exhibiting extraordinary thermoelectric properties. The well-ordered CoO2-terminated surface with random Na distribution was observed. However, lattice constants of the surface are smaller than that in bulk. The surface density of states (DOS) showed strong temperature dependence. Especially, an unusual shift of the minimum DOS occurs below 230 K, clearly indicating a local charging effect on the surface. ^ Cd2Re2O7 is the first known pyrochlore oxide superconductor (Tc ∼ 1K). It exhibited an unusual second-order phase transition occurring at TS1 = 200 K and a controversial first-order transition at TS2 = 120 K. While bulk properties display large anomalies at TS1 but rather subtle and sample-dependent changes at TS2, the surface DOS near the EF show no change at T s1 but a substantial increase below TS2---a complete reversal as the signature for the transitions. We argued that crystal imperfections, mainly defects, which were considerably enhanced at the surface, resulted in the transition at TS2. ^

Noise in gallium nitride-based quantum well structures used for nanometer devices in the frequency range 1 Hz--3 Mhz and temperature range 77K--324K

Electronic noise has been investigated in AlxGa1−x N/GaN Modulation-Doped Field Effect Transistors (MODFETs) of submicron dimensions, grown for us by MBE (Molecular Beam Epitaxy) techniques at Virginia Commonwealth University by Dr. H. Morkoç and coworkers. Some 20 devices were grown on a GaN substrate, four of which have leads bonded to source (S), drain (D), and gate (G) pads, respectively. Conduction takes place in the quasi-2D layer of the junction (xy plane) which is perpendicular to the quantum well (z-direction) of average triangular width ∼3 nm. A non-doped intrinsic buffer layer of ∼5 nm separates the Si-doped donors in the AlxGa1−xN layer from the 2D-transistor plane, which affords a very high electron mobility, thus enabling high-speed devices. Since all contacts (S, D, and G) must reach through the AlxGa1−xN layer to connect internally to the 2D plane, parallel conduction through this layer is a feature of all modulation-doped devices. While the shunting effect may account for no more than a few percent of the current IDS, it is responsible for most excess noise, over and above thermal noise of the device. ^ The excess noise has been analyzed as a sum of Lorentzian spectra and 1/f noise. The Lorentzian noise has been ascribed to trapping of the carriers in the AlxGa1−xN layer. A detailed, multitrapping generation-recombination noise theory is presented, which shows that an exponential relationship exists for the time constants obtained from the spectral components as a function of 1/kT. The trap depths have been obtained from Arrhenius plots of log (τT2) vs. 1000/T. Comparison with previous noise results for GaAs devices shows that: (a) many more trapping levels are present in these nitride-based devices; (b) the traps are deeper (farther below the conduction band) than for GaAs. Furthermore, the magnitude of the noise is strongly dependent on the level of depletion of the AlxGa1−xN donor layer, which can be altered by a negative or positive gate bias VGS. ^ Altogether, these frontier nitride-based devices are promising for bluish light optoelectronic devices and lasers; however, the noise, though well understood, indicates that the purity of the constituent layers should be greatly improved for future technological applications. ^

"New" Social Movements: Alternative Modernities, (Trans)local Nationalisms, and Solidarity Economies

My dissertation is the first project on the Haitian Platform for Advocacy for an Alternative Development- PAPDA, a nation-building coalition founded by activists from varying sectors to coordinate one comprehensive nationalist movement against what they are calling an Occupation. My work not only provides information on this under-theorized popular movement but also situates it within the broader literature on the postcolonial nation-state as well as Latin American and Caribbean social movements. The dissertation analyzes the contentious relationship between local and global discourses and practices of citizenship. Furthermore, the research draws on transnational feminist theory to underline the scattered hegemonies that intersect to produce varied spaces and practices of sovereignty within the Haitian postcolonial nation-state. The dissertation highlights how race and class, gender and sexuality, education and language, and religion have been imagined and co-constituted by Haitian social movements in constructing ‘new’ collective identities that collapse the private and the public, the rural and the urban, the traditional and the modern. My project complements the scholarship on social movements and the postcolonial nation-state and pushes it forward by emphasizing its spatial dimensions. Moreover, the dissertation de-centers the state to underline the movement of capital, goods, resources, and populations that shape the postcolonial experience. I re-define the postcolonial nation-state as a network of local, regional, international, and transnational arrangements between different political agents, including social movement actors. To conduct this interdisciplinary research project, I employed ethnographic methods, discourse and textual analysis, as well as basic mapping and statistical descriptions in order to present a historically-rooted interpretation of individual and organizational negotiations for community-based autonomy and regional development.

International tourism : can it contribute to Nigeria's economic growth as other industrial sectors?

The growth of international tourism and the attendant economic benefits to the world nations, has been phenominal since the end of the second world war. It is considered that the industry's upsurge will continue even in the phase of various constraints exemplified in high fuel cost, constant increase in fares and the threatening world-wide recessions. Developed as well as developing countries have gained substantially from the industry. A recent development shows increasing tourist traffic towards developing countries, while developed countries still hold their fort in stable growth of tourist receipts. The strategic beneficial effects of international tourist industry are often quantified in terms of foreign exchange earnings, employments offered, and the Real Estate super-structures; but in general,the industry has innumerable direct and indirect benefits to any nation engaging in the trade. The objective of this thesis is to demonstrate by comparative analysis and proven parameters that the international tourist industry which is given low priority in development in Nigeria, can equally contribute to the nation's economic growth as other industrial sectors which receive high priority and patronage in development. The data for this paper are gathered from primary sources which are i) responses by the Federal and State Governments' tourism-related offices; ii) government publications e.a. the Third National Development Plan of Federal Republic of Nigeria; and iii) Books and collections. The secondary sources include reports,periodicals and hospitality industry publications. To formally establish the international tourist industry in Nigeria, all the governments (Federal, State and Local) and the private sector in the country, should commence the development of the industry with research and feasibility studies, to be followed by proper planning at all levels and based on the result of the research and feasibility studies.

Resources use and conservation attitudes of local people in the Western Terai landscape, Nepal

Two protected areas: Royal Bardia National Park (RBNP) and Royal Suklaphanta Wildlife Reserve (RSWR) in the Western Terai, Nepal, are under threats due to present political turmoil, uncontrolled immigration, inefficient land reform policies and unsustainable resource use. I did a stratified random questionnaire survey of 234 households to determine how resource use patterns and problems influence conservation attitudes. Chi-square, Student's t, Mann-Whitney and Kruskal-Wallis tests, and multiple regression were used. There was spatio-temporal variability in resource use patterns and dependency. People were collecting eight and seven types of resources in RBNP and RSWR, respectively. However, people in RBNP were more dependent on resources than RSWR. In both areas, the problem of firewood is serious. The mean attitude score of RBNP (8.4 ± 1.44) was significantly higher than the score of RSWR (7.7 ± 1.66; t = 3.24, p = 0.0007). Conservation attitude was determined by variables such as participation in trainings, wildlife damage, and satisfaction towards user groups.

Sustaining culture through architecture : how can local, vernacular architectural principles be adapted to contemporary design in a village in Guyana

This thesis explores how architecture can adapt local vernacular design principles to contemporary building design in a rural setting. Vernacular buildings in Guyana present a unique and coherent set of design principles developed in response to climatic and cultural conditions. The concept of “habitus” proposed by philosopher Pierre Bourdieu describing the evolving nature of social culture was used to interpret Guyanese local buildings. These principles were then applied to the design of a Women’s Center in the village of Port Mourant on the east coast of Guyana. The design specifically interpreted the “bottom-house” of local Guyanese architecture, an inherently flexible transitional outdoor space beneath raised buildings. The design of the Women’s Center demonstrates how contemporary architectural design can respond to climatic requirements, local preferences and societal needs to support the local culture.

Selection and Passage of County Land Preservation Voter Referendum: The Role of Government

County jurisdictions in America are increasingly exercising self-government in the provision of public community services through the context of second order federalism. In states exercising this form of contemporary governance, county governments with “reformed” policy-making structures and professional management practices, have begun to rival or surpass municipalities in the delivery of local services with regional implications such as environmental protection (Benton 2002, 2003; Marando and Reeves, 1993). The voter referendum, a form of direct democracy, is an important component of county land preservation and environmental protection governmental policies. The recent growth and success of land preservation voter referendums nationwide reflects an increase in citizen participation in government and their desire to protect vacant land and its natural environment from threats of over-development, urbanization and sprawl, loss of open space and farmland, deterioration of ecosystems, and inadequate park and recreational amenities. The study’s design employs a sequential, mixed method. First, a quantitative approach employs the Heckman two-step model. It is fitted with variables for the non-random sample of 227 voter referendum counties and all non-voter referendum counties in the U.S. from 1988 to 2009. Second, the qualitative data collected from the in-depth investigation of three South Florida county case studies with twelve public administrator interviews is transformed for integration with the quantitative findings. The purpose of the qualitative method is to complement, explain and enrich the statistical analysis of county demographic, socio-economic, terrain, regional, governance and government, political preference, environmentalism, and referendum-specific factors. The research finds that government factors are significant in terms of the success of land preservation voter referendums; more specifically, the presence of self-government authority (home rule charter), a reformed structure (county administrator/manager or elected executive), and environmental interest groups. In addition, this study concludes that successful counties are often located coastal, exhibit population and housing growth, and have older and more educated citizens who vote democratic in presidential elections. The analysis of case study documents and public administrator interviews finds that pragmatic considerations of timing, local politics and networking of regional stakeholders are also important features of success. Further research is suggested utilizing additional public participation, local government and public administration factors.

Lower Aptian Comparative Stratigraphy of the Basco-Cantabrian Region (Spain) and Eastern Cordillera (Colombia): implications for local factors in the depositional record of Oceanic Anoxic Event 1a (OAE-1a)

An important episode of carbon sequestration, Oceanic Anoxic Event 1a (OAE-1a), characterizes the Lower Aptian worldwide, and is mostly known from deeper-water settings. The present work of two Lower Aptian deposits, Madotz (N Spain) and Curití Quarry (Colombia), is a multiproxy study that includes fossil assemblages, microfacies, X-ray diffraction bulk and clay mineralogy, elemental analyses (major, minor, trace elements), Rock-Eval pyrolysis, biomarkers, inorganic and organic carbon content, and stable carbon isotopes. The results provide baseline evidence of the local and global controlling environmental factors influencing OAE-1a in shallow-water settings. The data also improve our general understanding of the conditions under which organic-carbon-rich deposits accumulate. The sequence at Madotz includes four intervals (Unit 1; Subunits 2a, 2b and 2c) that overlap the times prior to, during and after the occurrence of OAE-1a. The Lower Unit 1(3m thick) is essentially siliciclastic, and Subunit 2a (20m) contains Urgonian carbonate facies that document abruptly changing platform conditions prior to OAE-1a. Subunit 2b (24.4 m) is a mixed carbonate-siliciclastic facies with orbitolinid-rich levels that coincides with OAE-1a δ13C stages C4-C6, and is coeval with the upper part of the Deshayesites forbesi ammonite zone. Levels with pyrite and the highest TOC values (0.4-0.97%), interpreted as accumulating under suboxic conditions, and are restricted to δ13C stages C4 and C5. The best development of the suboxic facies is at the level representing the peak of the transgression. Subunit 2c, within δ13C stage C7, shows a return of the Urgonian facies. The 23.35-m section at Curití includes a 6.3-m interval at the base of the Paja Formation dominated by organic-rich marlstones and shales lacking benthic fossils and bioturbation, with TOC values as high as 8.84%. The interval overlies a level containing reworked and phosphatized assemblages of middle Barremian to lowest Aptian ammonites. The range of values and the overall pattern of the δ13Corg (-22.05‰ to -20.47‰) in the 6.3m-interval is comparable with Lower Aptian δ13C stage C7. Thus, conditions of oxygen depletion at this site also occurred after Oceanic Anoxic Event-1a, which developed between carbon isotope stages C3 and C6. Both sites, Madotz and Curití, attest to the importance of terrigenous and nutrient fluxes in increasing OM productivity that led to episodic oxygen deficiency.

Reducing Uncertainties in Estimation of Wind Effects on Tall Buildings Using Aerodynamic Wind Tunnel Tests

Tall buildings are wind-sensitive structures and could experience high wind-induced effects. Aerodynamic boundary layer wind tunnel testing has been the most commonly used method for estimating wind effects on tall buildings. Design wind effects on tall buildings are estimated through analytical processing of the data obtained from aerodynamic wind tunnel tests. Even though it is widely agreed that the data obtained from wind tunnel testing is fairly reliable the post-test analytical procedures are still argued to have remarkable uncertainties. This research work attempted to assess the uncertainties occurring at different stages of the post-test analytical procedures in detail and suggest improved techniques for reducing the uncertainties. Results of the study showed that traditionally used simplifying approximations, particularly in the frequency domain approach, could cause significant uncertainties in estimating aerodynamic wind-induced responses. Based on identified shortcomings, a more accurate dual aerodynamic data analysis framework which works in the frequency and time domains was developed. The comprehensive analysis framework allows estimating modal, resultant and peak values of various wind-induced responses of a tall building more accurately. Estimating design wind effects on tall buildings also requires synthesizing the wind tunnel data with local climatological data of the study site. A novel copula based approach was developed for accurately synthesizing aerodynamic and climatological data up on investigating the causes of significant uncertainties in currently used synthesizing techniques. Improvement of the new approach over the existing techniques was also illustrated with a case study on a 50 story building. At last, a practical dynamic optimization approach was suggested for tuning structural properties of tall buildings towards attaining optimum performance against wind loads with less number of design iterations.