952 resultados para spectrum of transition operator
Resumo:
The energy spectrum of cosmic rays between 10(16) eV and 10(18) eV, derived from measurements of the shower size (total number of charged particles) and the total muon number of extensive air showers by the KASCADE-Grande experiment, is described. The resulting all-particle energy spectrum exhibits strong hints for a hardening of the spectrum at approximately 2 . 10(16) eV and a significant steepening at approximate to 8 . 10(16) eV. These observations challenge the view that the spectrum is a single power law between knee and ankle. Possible scenarios generating such features are discussed in terms of astrophysical processes that may explain the transition region from galactic to extragalactic origin of cosmic rays. (C) 2012 Elsevier B.V. All rights reserved.
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We theoretically study the resonance fluorescence spectrum of a three-level quantum emitter coupled to a spherical metallic nanoparticle. We consider the case that the quantum emitter is driven by a single laser field along one of the optical transitions. We show that the development of the spectrum depends on the relative orientation of the dipole moments of the optical transitions in relation to the metal nanoparticle. In addition, we demonstrate that the location and width of the peaks in the spectrum are strongly modified by the exciton-plasmon coupling and the laser detuning, allowing to achieve controlled strongly subnatural spectral line. A strong antibunching of the fluorescent photons along the undriven transition is also obtained. Our results may be used for creating a tunable source of photons which could be used for a probabilistic entanglement scheme in the field of quantum information processing.
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Although the transition metal chemistry of many dialkylamido ligands has been well studied, the chemistry of the bulky di(tert-butyl)amido ligand has been largely overlooked. The di(tert-butyl)amido ligand is well suited for synthesizing transition metal compounds with low coordination numbers; such compounds may exhibit interesting structural, physical, and chemical properties. Di(tert-butyl)amido complexes of transition metals are expected to exhibit high volatilities and low decomposition temperatures, thus making them well suited for the chemical vapor deposition of metals and metal nitrides. Treatment of MnBr₂(THF)₂, FeI₂, CoBr₂(DME), or NiBr₂(DME) with two equivalents of LiN(t-Bu)2 in benzene affords the two-coordinate complex M[N(t-Bu)₂]₂, where M is Mn, Fe, Co, or Ni. Crystallographic studies show that the M-N distances decrease across the series: 1.9365 (Mn), 1.8790 (Fe), 1.845 (Co), 1.798 Å (Ni). The N-M- N angles are very close to linear for Mn and Fe (179.30 and 179.45°, respectively), but bent for Co and Ni (159.2 and 160.90°, respectively). As expected, the d⁵ Mn complex has a magnetic moment of 5.53 μΒ that is very close to the spin only value. The EPR spectrum is nearly axial with a low E/D ratio of 0.014. The d⁶ Fe compound has a room temperature magnetic moment of 5.55 μΒ indicative of a large orbital angular momentum contribution. It does not exhibit a Jahn-Teller distortion despite the expected doubly degenerate ground state. Applied field Mössbauer spectroscopy shows that the effective internal hyperfine field is unusually large, Hint = 105 T. The magnetic moments of Co[N(t-Bu)₂]₂ and Ni[N(t-Bu)₂]₂ are 5.24 and 3.02 μΒ respectively. Both are EPR silent at 4.2 K. Treatment of TiCl₄ with three equivalents of LiN(t-Bu)2 in pentane affords the briding imido compound Ti₂[μ-N(t-Bu)]₂Cl₂[N(t-Bu)₂]₂ via a dealkylation reaction. Rotation around the bis(tert-butyl)amido groups is hindered, with activation parameters of ΔH‡ = 12.8 ± 0.6 kcal mol-1 and ΔS‡ = -8 ± 2 cal K-1 ·mol-1, as evidenced by variable temperature 1H NMR spectroscopy. Treatment of TiCl₄ with two equivalents of HN(t-Bu)₂ affords Ti₂Cl₆[N(t-Bu)₂]₂. This complex shows a close-contact of 2.634(3) Å between Ti and the carbon atom of one of the CH₃ substituents on the tert-butyl groups. Theoretical considerations and detailed structural comparisons suggest this interaction is not agostic in nature, but rather is a consequence of interligand repulsions. Treatment of NiI₂(PPh3)₂ and PdCl₂(PPh₃)₂ with LiN(t-Bu)₂in benzene affords Ni[N(t-Bu)₂](PPh₃)I and Pd₃(μ₂-NBut₂)2(μ₂-PPh₂)Ph(PPh₃) respectively. The compound Ni[N(t-Bu)₂](PPh₃)I has distorted T-shape in geometry, whereas Pd₃(μ₂-NBut₂)₂(μ₂-PPh₂)Ph(PPh₃) contains a triangular palladium core. Manganese nitride films were grown from Mn[N(t-Bu)₂]₂ in the presence of anhydrous ammonia. The growth rate was several nanometers per minute even at the remarkably low temperature of 80⁰C. As grown, the films are carbon- and oxygen-free, and have a columnar morphology. The spacings between the columns become smaller and the films become smoother as the growth temperature is increased. The composition of the films is consistent with a stoichiometry of Mn₅N₂.
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The Raman spectra at 77 K of the hydroxyl stretching of kaolinite were obtained along the three axes perpendicular to the crystal faces. Raman bands were observed at 3616, 3658 and 3677 cm−1 together with a distinct band observed at 3691 cm−1 and a broad profile between 3695 and 3715 cm−1. The band at 3616 cm−1 is assigned to the inner hydroxyl. The bands at 3658 and 3677 cm−1 are attributed to the out-of-phase vibrations of the inner surface hydroxyls. The Raman spectra of the in-phase vibrations of the inner-surface hydroxyl-stretching region are described in terms of transverse and longitudinal optic splitting. The band at 3691 cm−1 is assigned to the transverse optic and the broad profile to the longitudinal optic mode. This splitting remained even at liquid nitrogen temperature. The transverse optic vibration may be curve resolved into two or three bands, which are attributed to different types of hydroxyl groups in the kaolinite.
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The single crystal Raman spectra of minerals brandholzite and bottinoite, formula M[Sb(OH)6]2•6H2O, where M is Mg+2 and Ni+2 respectively, and the non-aligned Raman spectrum of mopungite, formula Na[Sb(OH)6], are presented for the first time. The mixed metal minerals comprise of alternating layers of [Sb(OH)6]-1 octahedra and mixed [M(H2O)6]+2 / [Sb(OH)6]-1 octahedra. Mopungite comprises hydrogen bonded layers of [Sb(OH)6]-1 octahedra linked within the layer by Na+ ions. The spectra of the three minerals were dominated by the Sb-O symmetric stretch of the [Sb(OH)6]-1 octahedron, which occurs at approximately 620 cm-1. The Raman spectrum of mopungite showed many similarities to spectra of the di-octahedral minerals informing the view that the Sb octahedra gave rise to most of the Raman bands observed, particularly below 1200 cm-1. Assignments have been proposed based on the spectral comparison between the minerals, prior literature and density field theory calculations of the vibrational spectra of the free [Sb(OH)6]-1 and [M(H2O)6]+2 octahedra by a model chemistry of B3LYP/6-31G(d) and lanl2dz for the Sb atom. The single crystal data spectra showed good mode separation, allowing the majority of the bands to be assigned a symmetry species of A or E.
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We report on analysis of discussions in an online community of people with chronic illness using socio-cognitively motivated, automatically produced semantic spaces. The analysis aims to further the emerging theory of "transition" (how people can learn to incorporate the consequences of illness into their lives). An automatically derived representation of sense of self for individuals is created in the semantic space by the analysis of the email utterances of the community members. The movement over time of the sense of self is visualised, via projection, with respect to axes of "ordinariness" and "extra-ordinariness". Qualitative evaluation shows that the visualisation is paralleled by the transitions of people during the course of their illness. The research aims to progress tools for analysis of textual data to promote greater use of tacit knowledge as found in online virtual communities. We hope it also encourages further interest in representation of sense-of-self.
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The current rapid urban growth throughout the world manifests in various ways and historically cities have grown, similarly, alternately or simultaneously between planned extensions and organic informal settlements (Mumford, 1989). Within cities different urban morphological regions can reveal different contexts of economic growth and/or periods of dramatic social/technological change (Whitehand, 2001, 105). Morpho-typological study of alternate contexts can present alternative models and contribute to the present discourse which questions traditional paradigms of urban planning and design (Todes et al, 2010). In this study a series of cities are examined as a preliminary exploration into the urban morphology of cities in ‘humid subtropical’ climates. From an initial set of twenty, six cities were selected: Sao Paulo, Brazil; Jacksonville, USA; Maputo, Mozambique; Kanpur, India; Hong Kong, China; and Brisbane, Australia. The urban form was analysed from satellite imagery at a constant scale. Urban morphological regions (types) were identified as those demonstrating particular consistant characteristics of form (density, typology and pattern) different to their surroundings when examined at a constant scale. This analysis was correlated against existing data and literature discussing the proliferation of two types of urban development, ‘informal settlement’ (defined here as self-organised communities identifiable but not always synonymous with ‘slums’) and ‘suburbia’ (defined here as master planned communities of generally detached houses prevalent in western society) - the extreme ends of a hypothetical spectrum from ‘planned’ to ‘spontaneous’ urban development. Preliminary results show some cities contain a wide variety of urban form ranging from the highly organic ‘self-organised’ type to the highly planned ‘master planned community’ (in the case of Sao Paulo) while others tend to fall at one end of the planning spectrum or the other (more planned in the cases of Brisbane and Jacksonville; and both highly planned and highly organic in the case of Maputo). Further research will examine the social, economical and political drivers and controls which lead to this diversity or homogeneity of urban form and speculates on the role of self-organisation as a process for the adaptation of urban form.
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In this paper, we report the preparation and characterisation of nanometer-sized TiO2, CdO, and ZnO semiconductor particles trapped in zeolite NaY. Preparation of these particles was carried out via the traditional ion exchange method and subsequent calcination procedure. It was found that the smaller cations, i.e., Cd2+ and Zn2+ could be readily introduced into the SI′ and SII′ sites located in the sodalite cages, through ion exchange; while this is not the case for the larger Ti species, i.e., Ti monomer [TiO]2+ or dimer [Ti2O3]2+ which were predominantly dispersed on the external surface of zeolite NaY. The subsequent calcination procedure promoted these Ti species to migrate into the internal surface of the supercages. These semiconductor particles confined in NaY zeolite host exhibited a significant blue shift in the UV-VIS absorption spectra, in contrast to the respective bulk semiconductor materials, due to the quantum size effect (QSE). The particle sizes calculated from the UV-VIS optical absorption spectra using the effective mass approximation model are in good agreement with the atomic absorption data.
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The design of concurrent software systems, in particular process-aware information systems, involves behavioral modeling at various stages. Recently, approaches to behavioral analysis of such systems have been based on declarative abstractions defined as sets of behavioral relations. However, these relations are typically defined in an ad-hoc manner. In this paper, we address the lack of a systematic exploration of the fundamental relations that can be used to capture the behavior of concurrent systems, i.e., co-occurrence, conflict, causality, and concurrency. Besides the definition of the spectrum of behavioral relations, which we refer to as the 4C spectrum, we also show that our relations give rise to implication lattices. We further provide operationalizations of the proposed relations, starting by proposing techniques for computing relations in unlabeled systems, which are then lifted to become applicable in the context of labeled systems, i.e., systems in which state transitions have semantic annotations. Finally, we report on experimental results on efficiency of the proposed computations.
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Background Adenocarcinoma of the esophagogastric junction (AEG) as described by Siewert et al. is classified as one entity in the latest (7th Edition) American Joint Cancer Committee/International Union Against Cancer (AJCC/UICC) manual, compared with the previous mix of esophageal and gastric staging systems. The origin of AEG tumors, esophageal or gastric, and their biology remain controversial, particularly for AEG type II (cardia) tumors. Methods We adapted a large prospective database (n = 520: 180 type I, 182 type II, 158 type III) to compare AEG tumors under the new TNM system Pathological variables associated with prognosis were compared (pT, pN, stage, differentiation, R status, lymphovascular invasion, perineural involvement, number of positive nodes, percent of positive nodes, and tumor length), as well as overall survival. Results Compared with AEG type I tumors, type II and type III tumors had significantly (p\0.05) more advanced pN stages, greater number and percentage of positive nodes, poorer differentiation, more radial margin involvement, and more perineural invasion. In AEG type I, 14/180 patients (8%) had[6 involved nodes (pN3), compared with 16 and 30% of patients classified type II and III, respectively. Median survival was significantly (p = 0.03) improved for type I patients (38 months) compared with those with tumors classified as type II (28 months) and type III (24 months). In multivariate analysis node positivity and pN staging but not AEG site had an impact on survival. Conclusions In this series AEG type I is associated with more favorable pathologic features and improved outcomes compared with AEG type II and III. This may reflect earlier diagnosis, but an alternative possibility, that type I may be a unique paradigm with more favorable biology, requires further study. © Société Internationale de Chirurgie 2010.
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In the expanding literature on creative practice research, art and design are often described as a unified field. They are bracketed together (art-and-design), referred to as interchangeable terms (art/design), and nested together, as if the practices of one domain encompass the other. However it is possible to establish substantial differences in research approaches. In this chapter we argue that core distinctions arise out of the goals of the research, intentions invested in the resulting “artefacts” (creative works, products, events), and the knowledge claims made for the research outcomes. Moreover, these fundamental differences give rise to a number of contingent attributes of the research such as the forming contexts, methodological approaches, and ways of evidencing and reporting new knowledge. We do not strictly ascribe these differences to disciplinary contexts. Rather, we use the terms effective practice research and evocative practice research to describe the spirit of the two distinctive research paradigms we identify. In short, effective practice research (often pursued in design fields) seeks a solution (or resolution) to a problem identified with a particular community, and it produces an artefact that addresses this problem by effecting change (making a situation, product or process more efficient or effective in some way). On the other hand, evocative practice research (often pursued by creative arts fields) is driven by individual pre-occupations, cultural concerns or human experience more broadly. It produces artefacts that evoke affect and resonance, and are poetically irreducible in meaning. We cite recent examples of creative research projects that illustrate the distinctions we identify. We then go on to describe projects that integrate these modes of research. In this way, we map out a creative research spectrum, with distinct poles as well as multiple hybrid possibilities. The hybrid projects we reference are not presented as evidence an undifferentiated field. Instead, we argue that they integrate research modes in deliberate, purposeful and distinctive ways: employing effective practice research methods in the production of evocative artefacts or harnessing evocative (as well as effective) research paradigms to effect change.
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Cyclostationary models for the diagnostic signals measured on faulty rotating machineries have proved to be successful in many laboratory tests and industrial applications. The squared envelope spectrum has been pointed out as the most efficient indicator for the assessment of second order cyclostationary symptoms of damages, which are typical, for instance, of rolling element bearing faults. In an attempt to foster the spread of rotating machinery diagnostics, the current trend in the field is to reach higher levels of automation of the condition monitoring systems. For this purpose, statistical tests for the presence of cyclostationarity have been proposed during the last years. The statistical thresholds proposed in the past for the identification of cyclostationary components have been obtained under the hypothesis of having a white noise signal when the component is healthy. This need, coupled with the non-white nature of the real signals implies the necessity of pre-whitening or filtering the signal in optimal narrow-bands, increasing the complexity of the algorithm and the risk of losing diagnostic information or introducing biases on the result. In this paper, the authors introduce an original analytical derivation of the statistical tests for cyclostationarity in the squared envelope spectrum, dropping the hypothesis of white noise from the beginning. The effect of first order and second order cyclostationary components on the distribution of the squared envelope spectrum will be quantified and the effectiveness of the newly proposed threshold verified, providing a sound theoretical basis and a practical starting point for efficient automated diagnostics of machine components such as rolling element bearings. The analytical results will be verified by means of numerical simulations and by using experimental vibration data of rolling element bearings.