9 resultados para Metal-to-metal-charge-transfer Band Energy

em Digital Commons at Florida International University


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Autism Spectrum Disorder () is defined as “the presence of severe and pervasive impairments in reciprocal social interaction and in verbal and nonverbal communication skills” (Diagnostic & Statistical Manual, 2000). It is estimated that 1 in 68 children across the United States are diagnosed with ASD. One of the most common delays that children diagnosed with ASD experience are language delays. Children with ASD that have a language delay will often develop maladaptive behaviors as a result of poor communication skills (Carr & Durand, 1985). The failure to develop mand acquisition in typical fashion results in behaviors ranging from social withdrawal to self-injurious behaviors (Cooper et. al, 2007). A lack of a strong tact repertoire can further impede and complicate the learning of other necessary components of language due to the inability to successfully label items and events in the physical environment of the child. The purpose of this study is to replicate with a reversal in verbal operant training of the procedures described in Wallace et al. (2006) in which two children with ASD underwent tact training to facilitate the formation of mands; essentially this study aims to accomplish mand training first to establish as tact. It is hypothesized that mand training will result in a greater repertoire of tacts due to strength of the relationship between mands and the control over the social environment (Cooper et al., 2007). The two children in the study will be taught to mand items that will be ranked in order of preference via stimulus preference assessment. This study is of great importance due to the indispensable value of effective social communication skills. Data gathered on improving communication skills is of great value to the ASD community as the implications for functional skills result in better communication with family and greater control of individual functioning.

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Autism Spectrum Disorder () is defined as “the presence of severe and pervasive impairments in reciprocal social interaction and in verbal and nonverbal communication skills” (Diagnostic & Statistical Manual, 2000). It is estimated that 1 in 68 children across the United States are diagnosed with ASD. One of the most common delays that children diagnosed with ASD experience are language delays. Children with ASD that have a language delay will often develop maladaptive behaviors as a result of poor communication skills (Carr & Durand, 1985). The failure to develop mand acquisition in typical fashion results in behaviors ranging from social withdrawal to self-injurious behaviors (Cooper et. al, 2007). A lack of a strong tact repertoire can further impede and complicate the learning of other necessary components of language due to the inability to successfully label items and events in the physical environment of the child. The purpose of this study is to replicate with a reversal in verbal operant training of the procedures described in Wallace et al. (2006) in which two children with ASD underwent tact training to facilitate the formation of mands; essentially this study aims to accomplish mand training first to establish as tact. It is hypothesized that mand training will result in a greater repertoire of tacts due to strength of the relationship between mands and the control over the social environment (Cooper et al., 2007). The two children in the study will be taught to mand items that will be ranked in order of preference via stimulus preference assessment. This study is of great importance due to the indispensable value of effective social communication skills. Data gathered on improving communication skills is of great value to the ASD community as the implications for functional skills result in better communication with family and greater control of individual functioning.

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Group VI metal hexacarbonyls, M(CO)6 (M = Cr, Mo and W), are of extreme importance as catalysts in industry and also of fundamental interest due to the established charge transfer mechanism between the carbon monoxide and the metal. They condense to molecular solids at ambient conditions retaining the octahedral (Oh) symmetry of gas phase and have been extensively investigated by previous workers to understand their fundamental chemical bonding and possible industrial applications. However little is known about their behavior at high pressures which is the focus of this dissertation. Metal hexacarbonyls were subjected to high pressures in Diamond-Anvil cells to understand the pressure effect on chemical bonding using Raman scattering in situ. The high-pressure results on each of the three metal hexacarbonyls are presented and are followed by a critical analysis of the entire family. The Raman study was conducted at pressures up to 45 GPa and X-ray up to 58 GPa. This is followed by a discussion on infra red spectra in conjunction with Raman and X-ray analysis to provide a rationale for polymerization. Finally the probable synthesis of extremely reactive species under high-pressures and as identified via Raman is discussed. The high-pressure Raman scattering, up to 30 GPa, demonstrated the absence of Π-backbonding. The disappearance of parental Raman spectra for (M = Cr, Mo and W) at 29.6, 23.3 and 22.2 GPa respectively was attributed to the total collapse of the Oh symmetry. This collapse under high-pressure lead to metal-mediated polymeric phase characterized by Raman active δ(OCO) feature, originating from intermolecular vibrational coupling in the parent sample. Further increase in pressures up to 45 GPa, did not affect this feature. The pressure quenched Raman spectra, revealed various chemical groups non-characteristic of the parent sample and adsorption of CO in addition to the characteristic δ(OCO) feature. The thus recorded Raman, complemented with the far and mid-infrared pressure quenched spectra, reveal the formation of novel metal-mediated polymers. The X-ray diffraction on W(CO)6 up to 58 GPa revealed the generation of amorphous polymeric pattern which was retained back to ambient conditions.

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In the current age of fast-depleting conventional energy sources, top priority is given to exploring non-conventional energy sources, designing highly efficient energy storage systems and converting existing machines/instruments/devices into energy-efficient ones. ‘Energy efficiency’ is one of the important challenges for today’s scientific and research community, worldwide. In line with this demand, the current research was focused on developing two highly energy-efficient devices – field emitters and Li-ion batteries, using beneficial properties of carbon nanotubes (CNT). Interface-engineered, directly grown CNTs were used as cathode in field emitters, while similar structure was applied as anode in Li-ion batteries. Interface engineering was found to offer minimum resistance to electron flow and strong bonding with the substrate. Both field emitters and Li-ion battery anodes were benefitted from these advantages, demonstrating high energy efficiency. Field emitter, developed during this research, could be characterized by low turn-on field, high emission current, very high field enhancement factor and extremely good stability during long-run. Further, application of 3-dimensional design to these field emitters resulted in achieving one of the highest emission current densities reported so far. The 3-D field emitter registered 27 times increase in current density, as compared to their 2-D counterparts. These achievements were further followed by adding new functionalities, transparency and flexibility, to field emitters, keeping in view of current demand for flexible displays. A CNT-graphene hybrid structure showed appreciable emission, along with very good transparency and flexibility. Li-ion battery anodes, prepared using the interface-engineered CNTs, have offered 140% increment in capacity, as compared to conventional graphite anodes. Further, it has shown very good rate capability and an exceptional ‘zero capacity degradation’ during long cycle operation. Enhanced safety and charge transfer mechanism of this novel anode structure could be explained from structural characterization. In an attempt to progress further, CNTs were coated with ultrathin alumina by atomic layer deposition technique. These alumina-coated CNT anodes offered much higher capacity and an exceptional rate capability, with very low capacity degradation in higher current densities. These highly energy efficient CNT based anodes are expected to enhance capacities of future Li-ion batteries.

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A high resolution study of the quasielastic 2 H(e, e'p)n reaction was performed in Hall A at the Thomas Jefferson Accelerator Facility in Newport News, Virginia. The measurements were performed at a central momentum transfer of : q: ∼ 2400 MeV/c, and at a central energy transfer of ω ∼ 1500 MeV, a four momentum transfer Q2 = 3.5 (GeV/c)2, covering missing momenta from 0 to 0.5 GeV/c. The majority of the measurements were performed at Φ = 180° and a small set of measurements were done at Φ = 0°. The Hall A High Resolution Spectrometers (HRS) were used to detect coincident electrons and protons, respectively. Absolute 2H(e, e'p) n cross sections were obtained as a function of the recoiling neutron scattering angle with respect to [special characters omitted]. The experimental results were compared to a Plane Wave Impulse Approximation (PWIA) model and to a calculation that includes Final State Interaction (FSI) effects. Experimental 2H(e, e'p)n cross sections were determined with an estimated systematic uncertainty of 7%. The general features of the measured cross sections are reproduced by Glauber based calculations that take the motion of the bound nucleons into account (GEA). Final State Interactions (FSI) contributions were found to depend strongly on the angle of the recoiling neutron with respect to the momentum transfer and on the missing momentum. We found a systematic deviation of the theoretical prediction of about 30%. At small &thetas; nq (&thetas;nq < 60°) the theory overpredicts the cross section while at large &thetas; nq (&thetas;nq > 80°) the theory underestimates the cross sections. We observed an enhancement of the cross section, due to FSI, of about 240%, as compared to PWIA, for a missing momentum of 0.4 GeV/c at an angle of 75°. For missing momentum of 0.5 GeV/c the enhancement of the cross section due to the same FSI effects, was about 270%. This is in agreement with GEA. Standard Glauber calculations predict this large contribution to occur at an angle of 90°. Our results show that GEA better describes the 2H(e, e'p)n reaction.

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Synthesis and functionalization of large-area graphene and its structural, electrical and electrochemical properties has been investigated. First, the graphene films, grown by thermal chemical vapor deposition (CVD), contain three to five atomic layers of graphene, as confirmed by Raman spectroscopy and high-resolution transmission electron microscopy. Furthermore, the graphene film is treated with CF4 reactive-ion plasma to dope fluorine ions into graphene lattice as confirmed by X-ray photoelectron spectroscopy (XPS) and UV-photoemission spectroscopy (UPS). Electrochemical characterization reveals that the catalytic activity of graphene for iodine reduction enhanced with increasing plasma treatment time, which is attributed to increase in catalytic sites of graphene for charge transfer. The fluorinated graphene is characterized as a counter-electrode (CE) in a dye-sensitized solar cell (DSSC) which shows ~ 2.56% photon to electron conversion efficiency with ~11 mAcm−2 current density. Second, the large scale graphene film is covalently functionalized with HNO3 for high efficiency electro-catalytic electrode for DSSC. The XPS and UPS confirm the covalent attachment of C-OH, C(O)OH and NO3- moieties with carbon atoms through sp2-sp3 hybridization and Fermi level shift of graphene occurs under different doping concentrations, respectively. Finally, CoS-implanted graphene (G-CoS) film was prepared using CVD followed by SILAR method. The G-CoS electro-catalytic electrodes are characterized in a DSSC CE and is found to be highly electro-catalytic towards iodine reduction with low charge transfer resistance (Rct ~5.05 Ωcm 2) and high exchange current density (J0~2.50 mAcm -2). The improved performance compared to the pristine graphene is attributed to the increased number of active catalytic sites of G-CoS and highly conducting path of graphene. We also studied the synthesis and characterization of graphene-carbon nanotube (CNT) hybrid film consisting of graphene supported by vertical CNTs on a Si substrate. The hybrid film is inverted and transferred to flexible substrates for its application in flexible electronics, demonstrating a distinguishable variation of electrical conductivity for both tension and compression. Furthermore, both turn-on field and total emission current was found to depend strongly on the bending radius of the film and were found to vary in ranges of 0.8 - 3.1 V/μm and 4.2 - 0.4 mA, respectively.

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Electrical energy is an essential resource for the modern world. Unfortunately, its price has almost doubled in the last decade. Furthermore, energy production is also currently one of the primary sources of pollution. These concerns are becoming more important in data-centers. As more computational power is required to serve hundreds of millions of users, bigger data-centers are becoming necessary. This results in higher electrical energy consumption. Of all the energy used in data-centers, including power distribution units, lights, and cooling, computer hardware consumes as much as 80%. Consequently, there is opportunity to make data-centers more energy efficient by designing systems with lower energy footprint. Consuming less energy is critical not only in data-centers. It is also important in mobile devices where battery-based energy is a scarce resource. Reducing the energy consumption of these devices will allow them to last longer and re-charge less frequently. Saving energy in computer systems is a challenging problem. Improving a system's energy efficiency usually comes at the cost of compromises in other areas such as performance or reliability. In the case of secondary storage, for example, spinning-down the disks to save energy can incur high latencies if they are accessed while in this state. The challenge is to be able to increase the energy efficiency while keeping the system as reliable and responsive as before. This thesis tackles the problem of improving energy efficiency in existing systems while reducing the impact on performance. First, we propose a new technique to achieve fine grained energy proportionality in multi-disk systems; Second, we design and implement an energy-efficient cache system using flash memory that increases disk idleness to save energy; Finally, we identify and explore solutions for the page fetch-before-update problem in caching systems that can: (a) control better I/O traffic to secondary storage and (b) provide critical performance improvement for energy efficient systems.

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E=MC³ Energy Equals Management's Continued Cost Concern, is an essay written by Fritz G. Hagenmeyer, Associate Professor, School of Hospitality Management at Florida International University. In the writing, Hagenmeyer initially tenders: “Energy problems in the hospitality industry can be contained or reduced, yielding elevated profits as a result of applied, quality management principles. The concepts, processes and procedures presented in this article are intended to aid present and future managers to become more effective with a sharpened focus on profitability.” This article is an overview of energy efficiency and the management of such. In an expanding energy consumption market with its escalating costs, energy management has become an ever increasing concern and component of responsible hospitality management, Hagenmeyer will have you know. “In endeavoring to "manage" on a day-to-day basis a functioning hospitality building's energy system, the person in charge must take on the role of Justice with her scales, attempting to balance the often varying comfort needs of guests and occupants with the invariable rising costs of energy utilized to generate and maintain such comfort conditions, since comfort is seen as an integral part of the "service," "product," or "price/value” perception of patrons,” says Hagenmeyer. In contrast to what was thought in the mid point of this century - that energy would be abundant and cheap - the reality has set-in that this is not the case; not by a long shot. The author wants you to be aware that energy costs in buildings are a force to be reckoned with; a major expense to be sure. “Since 1973, "energy-conscious design" has begun to become part of the repertoire of architects, design engineers, and construction companies,” Hagenmeyer states. “For instance, whereas office buildings of the early 1970s might have used 400,000 British Thermal Units (BTUs) per square foot year, new buildings are going up that use 55,000 to 65,000 BTUs per square foot year,” Hagenmeyer, like an incandescent bulb, illuminates you. Hagenmeyer references Robert E. Aulbach’s article - Energy Management – when informing you that the hospitality manager should not become complacent in addressing the energy cost issue, but should and must maintain a diligent focus on the problem. Hagenmeyer also makes reference to the Middle East War and to OPEC, and their influence on energy prices. In closing, Hagenmeyer suggests an - Energy Management Action Plan – which he outlines for you.

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Modern civilization has developed principally through man's harnessing of forces. For centuries man had to rely on wind, water and animal force as principal sources of power. The advent of the industrial revolution, electrification and the development of new technologies led to the application of wood, coal, gas, petroleum, and uranium to fuel new industries, produce goods and means of transportation, and generate the electrical energy which has become such an integral part of our lives. The geometric growth in energy consumption, coupled with the world's unrestricted growth in population, has caused a disproportionate use of these limited natural resources. The resulting energy predicament could have serious consequences within the next half century unless we commit ourselves to the philosophy of effective energy conservation and management. National legislation, along with the initiative of private industry and growing interest in the private sector has played a major role in stimulating the adoption of energy-conserving laws, technologies, measures, and practices. It is a matter of serious concern in the United States, where ninety-five percent of the commercial and industrial facilities which will be standing in the year 2000 - many in need of retrofit - are currently in place. To conserve energy, it is crucial to first understand how a facility consumes energy, how its users' needs are met, and how all internal and external elements interrelate. To this purpose, the major thrust of this report will be to emphasize the need to develop an energy conservation plan that incorporates energy auditing and surveying techniques. Numerous energy-saving measures and practices will be presented ranging from simple no-cost opportunities to capital intensive investments.