994 resultados para reaction window theory


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Speaker diarization is the process of annotating an input audio with information that attributes temporal regions of the audio signal to their respective sources, which may include both speech and non-speech events. For speech regions, the diarization system also specifies the locations of speaker boundaries and assign relative speaker labels to each homogeneous segment of speech. In short, speaker diarization systems effectively answer the question of ‘who spoke when’. There are several important applications for speaker diarization technology, such as facilitating speaker indexing systems to allow users to directly access the relevant segments of interest within a given audio, and assisting with other downstream processes such as summarizing and parsing. When combined with automatic speech recognition (ASR) systems, the metadata extracted from a speaker diarization system can provide complementary information for ASR transcripts including the location of speaker turns and relative speaker segment labels, making the transcripts more readable. Speaker diarization output can also be used to localize the instances of specific speakers to pool data for model adaptation, which in turn boosts transcription accuracies. Speaker diarization therefore plays an important role as a preliminary step in automatic transcription of audio data. The aim of this work is to improve the usefulness and practicality of speaker diarization technology, through the reduction of diarization error rates. In particular, this research is focused on the segmentation and clustering stages within a diarization system. Although particular emphasis is placed on the broadcast news audio domain and systems developed throughout this work are also trained and tested on broadcast news data, the techniques proposed in this dissertation are also applicable to other domains including telephone conversations and meetings audio. Three main research themes were pursued: heuristic rules for speaker segmentation, modelling uncertainty in speaker model estimates, and modelling uncertainty in eigenvoice speaker modelling. The use of heuristic approaches for the speaker segmentation task was first investigated, with emphasis placed on minimizing missed boundary detections. A set of heuristic rules was proposed, to govern the detection and heuristic selection of candidate speaker segment boundaries. A second pass, using the same heuristic algorithm with a smaller window, was also proposed with the aim of improving detection of boundaries around short speaker segments. Compared to single threshold based methods, the proposed heuristic approach was shown to provide improved segmentation performance, leading to a reduction in the overall diarization error rate. Methods to model the uncertainty in speaker model estimates were developed, to address the difficulties associated with making segmentation and clustering decisions with limited data in the speaker segments. The Bayes factor, derived specifically for multivariate Gaussian speaker modelling, was introduced to account for the uncertainty of the speaker model estimates. The use of the Bayes factor also enabled the incorporation of prior information regarding the audio to aid segmentation and clustering decisions. The idea of modelling uncertainty in speaker model estimates was also extended to the eigenvoice speaker modelling framework for the speaker clustering task. Building on the application of Bayesian approaches to the speaker diarization problem, the proposed approach takes into account the uncertainty associated with the explicit estimation of the speaker factors. The proposed decision criteria, based on Bayesian theory, was shown to generally outperform their non- Bayesian counterparts.

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Anisotropic damage distribution and evolution have a profound effect on borehole stress concentrations. Damage evolution is an irreversible process that is not adequately described within classical equilibrium thermodynamics. Therefore, we propose a constitutive model, based on non-equilibrium thermodynamics, that accounts for anisotropic damage distribution, anisotropic damage threshold and anisotropic damage evolution. We implemented this constitutive model numerically, using the finite element method, to calculate stress–strain curves and borehole stresses. The resulting stress–strain curves are distinctively different from linear elastic-brittle and linear elastic-ideal plastic constitutive models and realistically model experimental responses of brittle rocks. We show that the onset of damage evolution leads to an inhomogeneous redistribution of material properties and stresses along the borehole wall. The classical linear elastic-brittle approach to borehole stability analysis systematically overestimates the stress concentrations on the borehole wall, because dissipative strain-softening is underestimated. The proposed damage mechanics approach explicitly models dissipative behaviour and leads to non-conservative mud window estimations. Furthermore, anisotropic rocks with preferential planes of failure, like shales, can be addressed with our model.

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The practical number of charge carriers loaded is crucial to the evaluation of the capacity performance of carbon-based electrodes in service, and cannot be easily addressed experimentally. In this paper, we report a density functional theory study of charge carrier adsorption onto zigzag edge-shaped graphene nanoribbons (ZGNRs), both pristine and incorporating edge substitution with boron, nitrogen or oxygen atoms. All edge substitutions are found to be energetically favorable, especially in oxidized environments. The maximal loading of protons onto the substituted ZGNR edges obeys a rule of [8-n-1], where n is the number of valence electrons of the edge-site atom constituting the adsorption site. Hence, a maximum charge loading is achieved with boron substitution. This result correlates in a transparent manner with the electronic structure characteristics of the edge atom. The boron edge atom, characterized by the most empty p band, facilitates more than the other substitutional cases the accommodation of valence electrons transferred from the ribbon, induced by adsorption of protons. This result not only further confirms the possibility of enhancing charge storage performance of carbon-based electrochemical devices through chemical functionalization but also, more importantly, provides the physical rationale for further design strategies.

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Heteroatom doping on the edge of graphene may serve as an effective way to tune chemical activity of carbon-based electrodes with respect to charge carrier transfer in an aqueous environment. In a step towards developing mechanistic understanding of this phenomenon, we explore herein mechanisms of proton transfer from aqueous solution to pristine and doped graphene edges utilizing density functional theory. Atomic B-, N-, and O- doped edges as well as the native graphene are examined, displaying varying proton affinities and effective interaction ranges with the H3O+ charge carrier. Our study shows that the doped edges characterized by more dispersive orbitals, namely boron and nitrogen, demonstrate more energetically favourable charge carrier exchange compared with oxygen, which features more localized orbitals. Extended calculations are carried out to examine proton transfer from the hydronium ion in the presence of explicit water, with results indicating that the basic mechanistic features of the simpler model are unchanged.

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Density functional theory (DFT) calculations have been carried out to explore the catalytic activation of C–H bonds in methane by the iron atom, Fe, and the iron dimer, Fe2. For methane activation on an Fe atom, the calculations suggest that the activation of the first C–H bond is mediated via the triplet excited-state potential energy surface (PES), with initial excitation of Fe to the triplet state being necessary for the reaction to be energetically feasible. Compared with the breaking of the first C–H bond, the cleavage of the second C–H bond is predicted to involve a significantly higher barrier, which could explain experimental observations of the HFeCH3 complex rather than CH2FeH2 in the activation of methane by an Fe atom. For methane activation on an iron dimer, the cleavage of the first C–H bond is quite facile with a barrier only 11.2, 15.8 and 8.4 kcal/mol on the septet state energy surface at the B3LYP/6-311+G(2df,2dp), BPW91/6-311+G(2df,2dp) and M06/B3LYP level, respectively. Cleavage of the second C–H bond from HFe2CH3 involves a barrier calculated respectively as 18.0, 10.7 and 12.4 kcal/mol at the three levels. The results suggest that the elimination of hydrogen from the dihydrogen complex is a rate-determining step. Overall, our results indicate that the iron dimer Fe2 has a stronger catalytic effect on the activation of methane than the iron atom.

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This thematic issue on education and the politics of becoming focuses on how a Multiple Literacies Theory (MLT) plugs into practice in education. MLT does this by creating an assemblage between discourse, text, resonance and sensations. What does this produce? Becoming AND how one might live are the product of an assemblage (May, 2005; Semetsky, 2003). In this paper, MLT is the approach that explores the connection between educational theory and practice through the lens of an empirical study of multilingual children acquiring multiple writing systems simultaneously. The introduction explicates discourse, text, resonance, sensation and becoming. The second section introduces certain Deleuzian concepts that plug into MLT. The third section serves as an introduction to MLT. The fourth section is devoted to the study by way of a rhizoanalysis. Finally, drawing on the concept of the rhizome, this article exits with potential lines of flight opened by MLT. These are becomings which highlight the significance of this work in terms of transforming not only how literacies are conceptualized, especially in minority language contexts, but also how one might live.

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This project was a step forward in developing and evaluating a novel, mathematical model that can deduce the meaning of words based on their use in language. This model can be applied to a wide range of natural language applications, including the information seeking process most of us undertake on a daily basis.

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Boards of directors are key governancemechanisms in organizations and fulfill twomain tasks:monitoringmanagers and firm performance, and providing advice and access to resources. In spite of a wealth of researchmuch remains unknown about how boards attend to the two tasks. This study investigates whether organizational (firm profitability) and environmental factors (industry regulation) affect board task performance. The data combine CEOs' responses to a questionnaire, and archival data from a sample of large Italian firms. Findings show that past firm performance is negatively associatedwith board monitoring and advice tasks; greater industry regulation enhances perceived board task performance; board monitoring and advice tasks tend to reinforce each other, despite their theoretical and practical distinction.

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This research studies information systems that adapt to the context in which they are used and provides recommendations on how the design of such systems can be improved. This thesis covers the problem of context-awareness via two case studies in the insurance and transportation industries. The study highlights shortcomings in the understanding of the relationship between information systems and context. Furthermore, it presents a new, theory-informed approach to design, and provides guidance for system developers seeking to implement context-aware information systems.

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In 2010, six Threshold Learning Outcomes (TLOs) for law were developed by the Australian Learning and Teaching Council's Discipline Scholars: Law. The final of these outcomes, TLO 6, concerns self-management. This thesis examines strategies for implementing self-management in Australian legal education by first contextualising the development of TLO 6 in light of other relevant national and international developments in higher education, and secondly, analysing this learning outcome through the lens of Self-Determination Theory (SDT), an influential branch of educational psychology. It is argued that the central concept of autonomous self-regulation in SDT provides insights into factors that are relevant to law students’ capacities for long-term self-management, which is reinforced by analysis of the literature on law students’ distress. Accordingly, curriculum design that supports students’ autonomy may simultaneously promote students’ self-management capacities. The discussion of theoretical and practical perspectives on autonomy supportive curriculum design in this thesis thus illuminates potential pedagogical approaches for the implementation of TLO 6 in Australian legal curricula.

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Travelling wave phenomena are observed in many biological applications. Mathematical theory of standard reaction-diffusion problems shows that simple partial differential equations exhibit travelling wave solutions with constant wavespeed and such models are used to describe, for example, waves of chemical concentrations, electrical signals, cell migration, waves of epidemics and population dynamics. However, as in the study of cell motion in complex spatial geometries, experimental data are often not consistent with constant wavespeed. Non-local spatial models have successfully been used to model anomalous diffusion and spatial heterogeneity in different physical contexts. In this paper, we develop a fractional model based on the Fisher-Kolmogoroff equation and analyse it for its wavespeed properties, attempting to relate the numerical results obtained from our simulations to experimental data describing enteric neural crest-derived cells migrating along the intact gut of mouse embryos. The model proposed essentially combines fractional and standard diffusion in different regions of the spatial domain and qualitatively reproduces the behaviour of neural crest-derived cells observed in the caecum and the hindgut of mouse embryos during in vivo experiments.

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The interaction of water with the fluorine-covered (001) surface of anatase titanium dioxide (TiO2) has been studied within the framework of density functional theory (DFT). Our results show that water dissociation is unfavorable due to repulsive interactions between surface fluorine and oxygen. We also found that the reaction of hydrofluoric acid with a surface hydroxyl group to form a surface Ti–F bond is exothermic, while the removal of fluorine from the surface needs additional energy of about half an eV. Therefore, water molecules are predicted to remain intact at the interface with the F-terminated anatase (001).

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Amonia borane (AB) has been identified as a potential candidate highcapacity hydrogen storage material. This work probes the adsorption and dissociation of AB inside and outside single-walled carbon nanotubes (SWCNTs) within the framework of density functional theory. The dissociation barriers of AB have been calculated and compared with that of the isolated AB molecule. On the basis of the present calculations, no notable improvement results from SWCNT confinement; on the contrary, the dissociation barrier slightly increases with respect to isolated AB.

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Strong binding of isolated carbon dioxide (CO2) on aluminium nitride (AlN) single walled nanotubes is verified using two different functionals. Two optimized configurations corresponding to physisorption and chemisorption are linked by a low energy barrier, such that the chemisorbed state is accessible and thermodynamically favored at low temperatures. In contrast, N2 is found only to form a physisorbed complex with the AlN nanotube, suggesting the potential application of aluminium nitride based materials for CO2 fixation. The effect of nanotube diameter on gas adsorption properties is also discussed. The diameter is found to have an important effect on the chemisorption of CO2, but has little effect on the physisorption of either CO2 or N2.

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The adsorption of carbon dioxide and nitrogen molecules on aluminum nitride (AlN) nanostructures has been explored using first-principle computational methods. Optimized configurations corresponding to physisorption and, subsequentially, chemisorption of CO2 are identified, in contrast to N2, for which only a physisorption structure is found. Transition-state searches imply a low energy barrier between the physisorption and chemisorption states for CO2 such that the latter is accessible and thermodynamically favored at room temperature. The effective binding energy of the optimized chemisorption structure is apparently larger than those for other CO2 adsorptive materials, suggesting the potential for application of aluminum nitride nanostructures for carbon dioxide capture and storage.