968 resultados para fluctuating valence


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The level of demand for healthcare services can fluctuate quite strongly. Indeed, some parts of the healthcare service are renowned for having peaks of demand which challenge capacity. Dealing with fluctuations in demand is a common problem in many service industries. This article examines some of the strategies available for influencing the level of demand, including the use of price, communications and demand analysis. The article also outlines a wide variety of ways in which patients can be encouraged to be more tolerant of waiting to receive service from healthcare professionals. In particular, eight principles of waiting are discussed and illustrated in the context of healthcare services.

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The gamma-ray decay of excited states of the one-valence-proton nucleus Sb-133 has been studied using cold-neutron induced fission of U-235 and Pu-241 targets, during the EXILL campaign at the ILL reactor in Grenoble. By using a highly efficient HPGe array, coincidences between gamma-rays prompt with the fission event and those delayed up to several tens of microseconds were investigated, allowing to observe, for the first time, high-spin excited states above the 16.6 mu s isomer. Lifetimes analysis, performed by fast-timing techniques with LaBr3(Ce) scintillators, revealed a difference of almost two orders of magnitude in B(M1) strength for transitions between positive-parity medium-spin yrast states. The data are interpreted by a newly developed microscopic model which takes into account couplings between core excitations (both collective and non-collective) of the doubly magic nucleus Sn-132 and the valence proton, using Skyrme effective interaction in a consistent way. The results point to a fast change in the nature of particle-core excitations with increasing spin. (C) 2016 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY license.

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Raman spectra were recorded in the range 400–1800 cm−1 for a series of 15 mixed \[tetrakis(4-tert-butylphenyl)porphyrinato](2,3-naphthalocyaninato) rare earth double-deckers M(TBPP)(Nc) (M = Y; La–Lu except Pm) using laser excitation at 632.8 and 785 nm. Comparisons with bis(naphthalocyaninato) rare earth counterparts reveal that the vibrations of the metallonaphthalocyanine M(Nc) fragment dominate the Raman features of M(TBPP)(Nc). When excited with radiation of 632.8 nm, the most intense vibration appears at about 1595 cm−1, due to the naphthalene stretching. These complexes exhibit the marker Raman band for Nc•− as a medium-intense band in the range 1496–1507 cm−1, attributed to the coupling of pyrrole and aza stretching, while the marker Raman band of Nc2− in intermediate-valence Ce(TBPP)(Nc) appears as a strong band at 1493 cm−1 and is due to the isoindole stretchings. By contrast, when excited with radiation of 785 nm that is in close resonance with the main Q absorption band of the naphthalocyanine ligand, the ring radial vibrations at ca 680 and 735 cm−1 for MIII(TBPP)(Nc) are selectively intensified and are the most intense bands. For the cerium double-decker, the most intense vibration also acting as the marker Raman band of Nc2− appears at 1497 cm−1 with contributions from both pyrrole CC and aza CN stretches. The same vibrational modes show weak to medium intensity scattering at 1506–1509 cm−1 for MIII(TBPP)(Nc) and this is the marker Raman band of Nc•− when thus excited. The scatterings due to the Nc breathings, ring radial vibration, aza group stretchings, naphthalene stretchings, benzoisoindole stretchings and the coupling of pyrrole CC and aza CN stretchings in MIII(TBPP)(Nc) are all slightly blue shifted along with the decrease in rare earth ionic radius, confirming the effects of increased ring–ring interactions on the Raman characteristics of naphthalocyanine in the mixed ring double-deckers.

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We report a theoretical study of the multiple oxidation states (1+, 0, 1−, and 2−) of a meso,meso-linked diporphyrin, namely bis[10,15,20-triphenylporphyrinatozinc(II)-5-yl]butadiyne (4), using Time-Dependent Density Functional Theory (TDDFT). The origin of electronic transitions of singlet excited states is discussed in comparison to experimental spectra for the corresponding oxidation states of the close analogue bis{10,15,20-tris[3‘,5‘-di-tert-butylphenyl]porphyrinatozinc(II)-5-yl}butadiyne (3). The latter were measured in previous work under in situ spectroelectrochemical conditions. Excitation energies and orbital compositions of the excited states were obtained for these large delocalized aromatic radicals, which are unique examples of organic mixed-valence systems. The radical cations and anions of butadiyne-bridged diporphyrins such as 3 display characteristic electronic absorption bands in the near-IR region, which have been successfully predicted with use of these computational methods. The radicals are clearly of the “fully delocalized” or Class III type. The key spectral features of the neutral and dianionic states were also reproduced, although due to the large size of these molecules, quantitative agreement of energies with observations is not as good in the blue end of the visible region. The TDDFT calculations are largely in accord with a previous empirical model for the spectra, which was based simplistically on one-electron transitions among the eight key frontier orbitals of the C4 (1,4-butadiyne) linked diporphyrins.

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Since the 1980s, industries and researchers have sought to better understand the quality of services due to the rise in their importance (Brogowicz, Delene and Lyth 1990). More recent developments with online services, coupled with growing recognition of service quality (SQ) as a key contributor to national economies and as an increasingly important competitive differentiator, amplify the need to revisit our understanding of SQ and its measurement. Although ‘SQ’ can be broadly defined as “a global overarching judgment or attitude relating to the overall excellence or superiority of a service” (Parasuraman, Berry and Zeithaml 1988), the term has many interpretations. There has been considerable progress on how to measure SQ perceptions, but little consensus has been achieved on what should be measured. There is agreement that SQ is multi-dimensional, but little agreement as to the nature or content of these dimensions (Brady and Cronin 2001). For example, within the banking sector, there exist multiple SQ models, each consisting of varying dimensions. The existence of multiple conceptions and the lack of a unifying theory bring the credibility of existing conceptions into question, and beg the question of whether it is possible at some higher level to define SQ broadly such that it spans all service types and industries. This research aims to explore the viability of a universal conception of SQ, primarily through a careful re-visitation of the services and SQ literature. The study analyses the strengths and weaknesses of the highly regarded and widely used global SQ model (SERVQUAL) which reflects a single-level approach to SQ measurement. The SERVQUAL model states that customers evaluate SQ (of each service encounter) based on five dimensions namely reliability, assurance, tangibles, empathy and responsibility. SERVQUAL, however, failed to address what needs to be reliable, assured, tangible, empathetic and responsible. This research also addresses a more recent global SQ model from Brady and Cronin (2001); the B&C (2001) model, that has potential to be the successor of SERVQUAL in that it encompasses other global SQ models and addresses the ‘what’ questions that SERVQUAL didn’t. The B&C (2001) model conceives SQ as being multidimensional and multi-level; this hierarchical approach to SQ measurement better reflecting human perceptions. In-line with the initial intention of SERVQUAL, which was developed to be generalizable across industries and service types, this research aims to develop a conceptual understanding of SQ, via literature and reflection, that encompasses the content/nature of factors related to SQ; and addresses the benefits and weaknesses of various SQ measurement approaches (i.e. disconfirmation versus perceptions-only). Such understanding of SQ seeks to transcend industries and service types with the intention of extending our knowledge of SQ and assisting practitioners in understanding and evaluating SQ. The candidate’s research has been conducted within, and seeks to contribute to, the ‘IS-Impact’ research track of the IT Professional Services (ITPS) Research Program at QUT. The vision of the track is “to develop the most widely employed model for benchmarking Information Systems in organizations for the joint benefit of research and practice.” The ‘IS-Impact’ research track has developed an Information Systems (IS) success measurement model, the IS-Impact Model (Gable, Sedera and Chan 2008), which seeks to fulfill the track’s vision. Results of this study will help future researchers in the ‘IS-Impact’ research track address questions such as: • Is SQ an antecedent or consequence of the IS-Impact model or both? • Has SQ already been addressed by existing measures of the IS-Impact model? • Is SQ a separate, new dimension of the IS-Impact model? • Is SQ an alternative conception of the IS? Results from the candidate’s research suggest that SQ dimensions can be classified at a higher level which is encompassed by the B&C (2001) model’s 3 primary dimensions (interaction, physical environment and outcome). The candidate also notes that it might be viable to re-word the ‘physical environment quality’ primary dimension to ‘environment quality’ so as to better encompass both physical and virtual scenarios (E.g: web sites). The candidate does not rule out the global feasibility of the B&C (2001) model’s nine sub-dimensions, however, acknowledges that more work has to be done to better define the sub-dimensions. The candidate observes that the ‘expertise’, ‘design’ and ‘valence’ sub-dimensions are supportive representations of the ‘interaction’, physical environment’ and ‘outcome’ primary dimensions respectively. The latter statement suggests that customers evaluate each primary dimension (or each higher level of SQ classification) namely ‘interaction’, physical environment’ and ‘outcome’ based on the ‘expertise’, ‘design’ and ‘valence’ sub-dimensions respectively. The ability to classify SQ dimensions at a higher level coupled with support for the measures that make up this higher level, leads the candidate to propose the B&C (2001) model as a unifying theory that acts as a starting point to measuring SQ and the SQ of IS. The candidate also notes, in parallel with the continuing validation and generalization of the IS-Impact model, that there is value in alternatively conceptualizing the IS as a ‘service’ and ultimately triangulating measures of IS SQ with the IS-Impact model. These further efforts are beyond the scope of the candidate’s study. Results from the candidate’s research also suggest that both the disconfirmation and perceptions-only approaches have their merits and the choice of approach would depend on the objective(s) of the study. Should the objective(s) be an overall evaluation of SQ, the perceptions-only approached is more appropriate as this approach is more straightforward and reduces administrative overheads in the process. However, should the objective(s) be to identify SQ gaps (shortfalls), the (measured) disconfirmation approach is more appropriate as this approach has the ability to identify areas that need improvement.

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When communicating emotion in music, composers and performers encode their expressive intentions through the control of basic musical features such as: pitch, loudness, timbre, mode, and articulation. The extent to which emotion can be controlled through the systematic manipulation of these features has not been fully examined. In this paper we present CMERS, a Computational Music Emotion Rule System for the control of perceived musical emotion that modifies features at the levels of score and performance in real-time. CMERS performance was evaluated in two rounds of perceptual testing. In experiment I, 20 participants continuously rated the perceived emotion of 15 music samples generated by CMERS. Three music works, each with five emotional variations were used (normal, happy, sad, angry, and tender). The intended emotion by CMERS was correctly identified 78% of the time, with significant shifts in valence and arousal also recorded, regardless of the works’ original emotion.

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Object tracking systems require accurate segmentation of the objects from the background for effective tracking. Motion segmentation or optical flow can be used to segment incoming images. Whilst optical flow allows multiple moving targets to be separated based on their individual velocities, optical flow techniques are prone to errors caused by changing lighting and occlusions, both common in a surveillance environment. Motion segmentation techniques are more robust to fluctuating lighting and occlusions, but don't provide information on the direction of the motion. In this paper we propose a combined motion segmentation/optical flow algorithm for use in object tracking. The proposed algorithm uses the motion segmentation results to inform the optical flow calculations and ensure that optical flow is only calculated in regions of motion, and improve the performance of the optical flow around the edge of moving objects. Optical flow is calculated at pixel resolution and tracking of flow vectors is employed to improve performance and detect discontinuities, which can indicate the location of overlaps between objects. The algorithm is evaluated by attempting to extract a moving target within the flow images, given expected horizontal and vertical movement (i.e. the algorithms intended use for object tracking). Results show that the proposed algorithm outperforms other widely used optical flow techniques for this surveillance application.

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Delirium is a disorder of acute onset with fluctuating symptoms and is characterized by inattention, disorganized thinking, and altered levels of consciousness. The risk for delirium is greatest in individuals with dementia, and the incidence of both is increasing worldwide because of the aging of our population. Although several clinical trials have tested interventions for delirium prevention in individuals without dementia, little is known about the mechanisms for the prevention of delirium in early-stage Alzheimer’s disease (AD). The purpose of this article is to explore ways of preventing delirium and slowing the rate of cognitive decline in early-stage AD by enhancing cognitive reserve. An agenda for future research on interventions to prevent delirium in individuals with early-stage AD is also presented.

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An experimental investigation has been made of a round, non-buoyant plume of nitric oxide, NO, in a turbulent grid flow of ozone, 03, using the Turbulent Smog Chamber at the University of Sydney. The measurements have been made at a resolution not previously reported in the literature. The reaction is conducted at non-equilibrium so there is significant interaction between turbulent mixing and chemical reaction. The plume has been characterized by a set of constant initial reactant concentration measurements consisting of radial profiles at various axial locations. Whole plume behaviour can thus be characterized and parameters are selected for a second set of fixed physical location measurements where the effects of varying the initial reactant concentrations are investigated. Careful experiment design and specially developed chemilurninescent analysers, which measure fluctuating concentrations of reactive scalars, ensure that spatial and temporal resolutions are adequate to measure the quantities of interest. Conserved scalar theory is used to define a conserved scalar from the measured reactive scalars and to define frozen, equilibrium and reaction dominated cases for the reactive scalars. Reactive scalar means and the mean reaction rate are bounded by frozen and equilibrium limits but this is not always the case for the reactant variances and covariances. The plume reactant statistics are closer to the equilibrium limit than those for the ambient reactant. The covariance term in the mean reaction rate is found to be negative and significant for all measurements made. The Toor closure was found to overestimate the mean reaction rate by 15 to 65%. Gradient model turbulent diffusivities had significant scatter and were not observed to be affected by reaction. The ratio of turbulent diffusivities for the conserved scalar mean and that for the r.m.s. was found to be approximately 1. Estimates of the ratio of the dissipation timescales of around 2 were found downstream. Estimates of the correlation coefficient between the conserved scalar and its dissipation (parallel to the mean flow) were found to be between 0.25 and the significant value of 0.5. Scalar dissipations for non-reactive and reactive scalars were found to be significantly different. Conditional statistics are found to be a useful way of investigating the reactive behaviour of the plume, effectively decoupling the interaction of chemical reaction and turbulent mixing. It is found that conditional reactive scalar means lack significant transverse dependence as has previously been found theoretically by Klimenko (1995). It is also found that conditional variance around the conditional reactive scalar means is relatively small, simplifying the closure for the conditional reaction rate. These properties are important for the Conditional Moment Closure (CMC) model for turbulent reacting flows recently proposed by Klimenko (1990) and Bilger (1993). Preliminary CMC model calculations are carried out for this flow using a simple model for the conditional scalar dissipation. Model predictions and measured conditional reactive scalar means compare favorably. The reaction dominated limit is found to indicate the maximum reactedness of a reactive scalar and is a limiting case of the CMC model. Conventional (unconditional) reactive scalar means obtained from the preliminary CMC predictions using the conserved scalar p.d.f. compare favorably with those found from experiment except where measuring position is relatively far upstream of the stoichiometric distance. Recommendations include applying a full CMC model to the flow and investigations both of the less significant terms in the conditional mean species equation and the small variation of the conditional mean with radius. Forms for the p.d.f.s, in addition to those found from experiments, could be useful for extending the CMC model to reactive flows in the atmosphere.

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When classifying a signal, ideally we want our classifier to trigger a large response when it encounters a positive example and have little to no response for all other examples. Unfortunately in practice this does not occur with responses fluctuating, often causing false alarms. There exists a myriad of reasons why this is the case, most notably not incorporating the dynamics of the signal into the classification. In facial expression recognition, this has been highlighted as one major research question. In this paper we present a novel technique which incorporates the dynamics of the signal which can produce a strong response when the peak expression is found and essentially suppresses all other responses as much as possible. We conducted preliminary experiments on the extended Cohn-Kanade (CK+) database which shows its benefits. The ability to automatically and accurately recognize facial expressions of drivers is highly relevant to the automobile. For example, the early recognition of “surprise” could indicate that an accident is about to occur; and various safeguards could immediately be deployed to avoid or minimize injury and damage. In this paper, we conducted initial experiments on the extended Cohn-Kanade (CK+) database which shows its benefits.

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Power transformers are one of the most important and costly equipment in power generation, transmission and distribution systems. Current average age of transformers in Australia is around 25 years and there is a strong economical tendency to use them up to 50 years or more. As the transformers operate, they get degraded due to different loading and environmental operating stressed conditions. In today‘s competitive energy market with the penetration of distributed energy sources, the transformers are stressed more with minimum required maintenance. The modern asset management program tries to increase the usage life time of power transformers with prognostic techniques using condition indicators. In the case of oil filled transformers, condition monitoring methods based on dissolved gas analysis, polarization studies, partial discharge studies, frequency response analysis studies to check the mechanical integrity, IR heat monitoring and other vibration monitoring techniques are in use. In the current research program, studies have been initiated to identify the degradation of insulating materials by the electrical relaxation technique known as dielectrometry. Aging leads to main degradation products like moisture and other oxidized products due to fluctuating thermal and electrical loading. By applying repetitive low frequency high voltage sine wave perturbations in the range of 100 to 200 V peak across available terminals of power transformer, the conductive and polarization parameters of insulation aging are identified. An in-house novel digital instrument is developed to record the low leakage response of repetitive polarization currents in three terminals configuration. The technique is tested with known three transformers of rating 5 kVA or more. The effects of stressing polarization voltage level, polarizing wave shapes and various terminal configurations provide characteristic aging relaxation information. By using different analyses, sensitive parameters of aging are identified and it is presented in this thesis.

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The dominant economic paradigm currently guiding industry policy making in Australia and much of the rest of the world is the neoclassical approach. Although neoclassical theories acknowledge that growth is driven by innovation, such innovation is exogenous to their standard models and hence often not explored. Instead the focus is on the allocation of scarce resources, where innovation is perceived as an external shock to the system. Indeed, analysis of innovation is largely undertaken by other disciplines, such as evolutionary economics and institutional economics. As more has become known about innovation processes, linear models, based on research and development or market demand, have been replaced by more complex interactive models which emphasise the existence of feedback loops between the actors and activities involved in the commercialisation of ideas (Manley 2003). Currently dominant among these approaches is the national or sectoral innovation system model (Breschi and Malerba 2000; Nelson 1993), which is based on the notion of increasingly open innovation systems (Chesbrough, Vanhaverbeke, and West 2008). This chapter reports on the ‘BRITE Survey’ funded by the Cooperative Research Centre for Construction Innovation which investigated the open sectoral innovation system operating in the Australian construction industry. The BRITE Survey was undertaken in 2004 and it is the largest construction innovation survey ever conducted in Australia. The results reported here give an indication of how construction innovation processes operate, as an example that should be of interest to international audiences interested in construction economics. The questionnaire was based on a broad range of indicators recommended in the OECD’s Community Innovation Survey guidelines (OECD/Eurostat 2005). Although the ABS has recently begun to undertake regular innovation surveys that include the construction industry (2006), they employ a very narrow definition of the industry and only collect very basic data compared to that provided by the BRITE Survey, which is presented in this chapter. The term ‘innovation’ is defined here as a new or significantly improved technology or organisational practice, based broadly on OECD definitions (OECD/Eurostat 2005). Innovation may be technological or organisational in nature and it may be new to the world, or just new to the industry or the business concerned. The definition thus includes the simple adoption of existing technological and organisational advancements. The survey collected information about respondents’ perceptions of innovation determinants in the industry, comprising various aspects of business strategy and business environment. It builds on a pilot innovation survey undertaken by PricewaterhouseCoopers (PWC) for the Australian Construction Industry Forum on behalf of the Australian Commonwealth Department of Industry Tourism and Resources, in 2001 (PWC 2002). The survey responds to an identified need within the Australian construction industry to have accurate and timely innovation data upon which to base effective management strategies and public policies (Focus Group 2004).

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The Sascha-Pelligrini low-sulphidation epithermal system is located on the western edge of the Deseado Massif, Santa Cruz Province, Argentina. Outcrop sampling has returned values of up to 160g/t gold and 796g/t silver, with Mirasol Resources and Coeur D.Alene Mines currently exploring the property. Detailed mapping of the volcanic stratigraphy has defined three units that comprise the middle Jurassic Chon Aike Formation and two units that comprise the upper Jurassic La Matilde Formation. The Chon Aike Formation consists of rhyodacite ignimbrites and tuffs, with the La Matilde Formation including rhyolite ash and lithic tuffs. The volcanic sequence is intruded by a large flow-banded rhyolite dome, with small, spatially restricted granodiorite dykes and sills cropping out across the study area. ASTER multispectral mineral mapping, combined with PIMA (Portable Infrared Mineral Analyser) and XRD (X-ray diffraction) analysis defines an alteration pattern that zones from laumontite-montmorillonite, to illite-pyritechlorite, followed by a quartz-illite-smectite-pyrite-adularia vein selvage. Supergene kaolinite and steam-heated acid-sulphate kaolinite-alunite-opal alteration horizons crop out along the Sascha Vein trend and Pelligrini respectively. Paragenetically, epithermal veining varies from chalcedonic to saccharoidal with minor bladed textures, colloform/crustiform-banded with visible electrum and acanthite, crustiform-banded grey chalcedonic to jasperoidal with fine pyrite, and crystalline comb quartz. Geothermometry of mineralised veins constrains formation temperatures from 174.8 to 205.1¡ÆC and correlates with the stability field for the interstratified illite-smectite vein selvage. Vein morphology, mineralogy and associated alteration are controlled by host rock rheology, permeability, and depth of the palaeo-water table. Mineralisation within ginguro banded veins resulted from fluctuating fluid pH associated with selenide-rich magmatic pulses, pressure release boiling and wall-rock silicate buffering. The study of the Sascha-Pelligrini epithermal system will form the basis for a deposit-specific model helping to clarify the current understanding of epithermal deposits, and may serve as a template for exploration of similar epithermal deposits throughout Santa Cruz.

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Objectives To explore the extent of and factors associated with male residents who change wandering status post nursing home admission. Design Longitudinal design with secondary data analyses. Admissions over a 4-year period were examined using repeat assessments with the Minimum Data Set (MDS) to formulate a model understanding the development of wandering behavior. Setting One hundred thirty-four Veterans Administration (VA) nursing homes throughout the United States. Participants: Included 6673 residents admitted to VA nursing homes between October 2000 and October 2004. Measurements MDS variables (cognitive impairment, mood, behavior problems, activities of daily living and wandering) included ratings recorded at residents’ admission to the nursing home and a minimum of two other time points at quarterly intervals. Results The majority (86%) of the sample were classified as non wanderers at admission and most of these (94%) remained non wanderers until discharge or the end of the study. Fifty one per cent of the wanderers changed status to non wanderers with 6% of these residents fluctuating in status more than two times. Admission variables associated with an increased risk of changing status from non-wandering to wandering included older age, greater cognitive impairment, more socially inappropriate behavior, resisting care, easier distractibility, and needing less help with personal hygiene. Requiring assistance with locomotion and having three or more medical comorbidities were associated with a decreased chance of changing from non-wandering to wandering status. Conclusion A resident’s change from non-wandering to wandering status may reflect an undetected medical event that affects cognition, but spares mobility.