973 resultados para Zeeman splitting
Resumo:
Since the conclusion of its 14-year civil war in 2003, Liberia has struggled economically. Jobs are in short supply and operational infrastructural services, such as electricity and running water, are virtually nonexistent. The situation has proved especially challenging for the scores of people who fled the country in the 1990s to escape the violence and who have since returned to re-enter their lives. With few economic prospects on hand, many have elected to enter the artisanal diamond mining sector, which has earned notoriety for perpetuating the country's civil war. This article critically reflects on the fate of these Liberians, many of whom, because of a lack of government support, finances, manpower and technological resources, have forged deals with hired labourers to work artisanal diamond fields. Specifically, in exchange for meals containing locally grown rice and a Maggi (soup) cube, hired hands mine diamondiferous territories, splitting the revenues accrued from the sales of recovered stones amongst themselves and the individual ‘claimholder’ who hired them. Although this cycle—referred to here as ‘diamond mining, rice farming and a Maggi cube’—helps to buffer against poverty, few of the parties involved will ever progress beyond a subsistence level
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In this paper the authors exploit two equivalent formulations of the average rate of material entropy production in the climate system to propose an approximate splitting between contributions due to vertical and eminently horizontal processes. This approach is based only on 2D radiative fields at the surface and at the top of atmosphere. Using 2D fields at the top of atmosphere alone, lower bounds to the rate of material entropy production and to the intensity of the Lorenz energy cycle are derived. By introducing a measure of the efficiency of the planetary system with respect to horizontal thermodynamic processes, it is possible to gain insight into a previous intuition on the possibility of defining a baroclinic heat engine extracting work from the meridional heat flux. The approximate formula of the material entropy production is verified and used for studying the global thermodynamic properties of climate models (CMs) included in the Program for Climate Model Diagnosis and Intercomparison (PCMDI)/phase 3 of the Coupled Model Intercomparison Project (CMIP3) dataset in preindustrial climate conditions. It is found that about 90% of the material entropy production is due to vertical processes such as convection, whereas the large-scale meridional heat transport contributes to only about 10% of the total. This suggests that the traditional two-box models used for providing a minimal representation of entropy production in planetary systems are not appropriate, whereas a basic—but conceptually correct—description can be framed in terms of a four-box model. The total material entropy production is typically 55 mW m−2 K−1, with discrepancies on the order of 5%, and CMs’ baroclinic efficiencies are clustered around 0.055. The lower bounds on the intensity of the Lorenz energy cycle featured by CMs are found to be around 1.0–1.5 W m−2, which implies that the derived inequality is rather stringent. When looking at the variability and covariability of the considered thermodynamic quantities, the agreement among CMs is worse, suggesting that the description of feedbacks is more uncertain. The contributions to material entropy production from vertical and horizontal processes are positively correlated, so that no compensation mechanism seems in place. Quite consistently among CMs, the variability of the efficiency of the system is a better proxy for variability of the entropy production due to horizontal processes than that of the large-scale heat flux. The possibility of providing constraints on the 3D dynamics of the fluid envelope based only on 2D observations of radiative fluxes seems promising for the observational study of planets and for testing numerical models.
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With extreme variability of the Arctic polar vortex being a key link for stratosphere–troposphere influences, its evolution into the twenty-first century is important for projections of changing surface climate in response to greenhouse gases. Variability of the stratospheric vortex is examined using a state-of-the-art climate model and a suite of specifically developed vortex diagnostics. The model has a fully coupled ocean and a fully resolved stratosphere. Analysis of the standard stratospheric zonal mean wind diagnostic shows no significant increase over the twenty-first century in the number of major sudden stratospheric warmings (SSWs) from its historical value of 0.7 events per decade, although the monthly distribution of SSWs does vary, with events becoming more evenly dispersed throughout the winter. However, further analyses using geometric-based vortex diagnostics show that the vortex mean state becomes weaker, and the vortex centroid is climatologically more equatorward by up to 2.5°, especially during early winter. The results using these diagnostics not only characterize the vortex structure and evolution but also emphasize the need for vortex-centric diagnostics over zonally averaged measures. Finally, vortex variability is subdivided into wave-1 (displaced) and -2 (split) components, and it is implied that vortex displacement events increase in frequency under climate change, whereas little change is observed in splitting events.
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We present a new iterative approach called Line Adaptation for the Singular Sources Objective (LASSO) to object or shape reconstruction based on the singular sources method (or probe method) for the reconstruction of scatterers from the far-field pattern of scattered acoustic or electromagnetic waves. The scheme is based on the construction of an indicator function given by the scattered field for incident point sources in its source point from the given far-field patterns for plane waves. The indicator function is then used to drive the contraction of a surface which surrounds the unknown scatterers. A stopping criterion for those parts of the surfaces that touch the unknown scatterers is formulated. A splitting approach for the contracting surfaces is formulated, such that scatterers consisting of several separate components can be reconstructed. Convergence of the scheme is shown, and its feasibility is demonstrated using a numerical study with several examples.
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Reaction of 5,6-dihydro-5,6-epoxy-1,10-phenanthroline (L) with Ni(ClO4)(2)center dot 6H(2)O in methanol in 3:1 M proportion at room temperature yields [NiL3](ClO4)(2)center dot 2H(2)O. The X-ray crystal structure of the cation Nil(3)(2+) has been determined. Aminolysis of the three epoxide rings in NiL32+ by 4-substituted anilines in boiling water without any Lewis acid catalyst gives a family of Ni(II) complexes with octahedral NiL62+ core. In these complexes, crystal field splitting 10Dq varies from 11601 to 15798 cm(-1) in acetonitrile. The variation in 10Dq is found to be satisfactorily linear (r(2) = 0.951) with the Hammett sigma(R) parameter of the substituent on the anilino fragment. 10Dq increases with the increase in the electron donation ability of the substituent.
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A two-stage linear-in-the-parameter model construction algorithm is proposed aimed at noisy two-class classification problems. The purpose of the first stage is to produce a prefiltered signal that is used as the desired output for the second stage which constructs a sparse linear-in-the-parameter classifier. The prefiltering stage is a two-level process aimed at maximizing a model's generalization capability, in which a new elastic-net model identification algorithm using singular value decomposition is employed at the lower level, and then, two regularization parameters are optimized using a particle-swarm-optimization algorithm at the upper level by minimizing the leave-one-out (LOO) misclassification rate. It is shown that the LOO misclassification rate based on the resultant prefiltered signal can be analytically computed without splitting the data set, and the associated computational cost is minimal due to orthogonality. The second stage of sparse classifier construction is based on orthogonal forward regression with the D-optimality algorithm. Extensive simulations of this approach for noisy data sets illustrate the competitiveness of this approach to classification of noisy data problems.
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Many operational weather forecasting centres use semi-implicit time-stepping schemes because of their good efficiency. However, as computers become ever more parallel, horizontally explicit solutions of the equations of atmospheric motion might become an attractive alternative due to the additional inter-processor communication of implicit methods. Implicit and explicit (IMEX) time-stepping schemes have long been combined in models of the atmosphere using semi-implicit, split-explicit or HEVI splitting. However, most studies of the accuracy and stability of IMEX schemes have been limited to the parabolic case of advection–diffusion equations. We demonstrate how a number of Runge–Kutta IMEX schemes can be used to solve hyperbolic wave equations either semi-implicitly or HEVI. A new form of HEVI splitting is proposed, UfPreb, which dramatically improves accuracy and stability of simulations of gravity waves in stratified flow. As a consequence it is found that there are HEVI schemes that do not lose accuracy in comparison to semi-implicit ones. The stability limits of a number of variations of trapezoidal implicit and some Runge–Kutta IMEX schemes are found and the schemes are tested on two vertical slice cases using the compressible Boussinesq equations split into various combinations of implicit and explicit terms. Some of the Runge–Kutta schemes are found to be beneficial over trapezoidal, especially since they damp high frequencies without dropping to first-order accuracy. We test schemes that are not formally accurate for stiff systems but in stiff limits (nearly incompressible) and find that they can perform well. The scheme ARK2(2,3,2) performs the best in the tests.
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We propose a new sparse model construction method aimed at maximizing a model’s generalisation capability for a large class of linear-in-the-parameters models. The coordinate descent optimization algorithm is employed with a modified l1- penalized least squares cost function in order to estimate a single parameter and its regularization parameter simultaneously based on the leave one out mean square error (LOOMSE). Our original contribution is to derive a closed form of optimal LOOMSE regularization parameter for a single term model, for which we show that the LOOMSE can be analytically computed without actually splitting the data set leading to a very simple parameter estimation method. We then integrate the new results within the coordinate descent optimization algorithm to update model parameters one at the time for linear-in-the-parameters models. Consequently a fully automated procedure is achieved without resort to any other validation data set for iterative model evaluation. Illustrative examples are included to demonstrate the effectiveness of the new approaches.
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A strong link exists between stratospheric variability and anomalous weather patterns at the earth’s surface. Specifically, during extreme variability of the Arctic polar vortex termed a “weak vortex event,” anomalies can descend from the upper stratosphere to the surface on time scales of weeks. Subsequently the outbreak of cold-air events have been noted in high northern latitudes, as well as a quadrupole pattern in surface temperature over the Atlantic and western European sectors, but it is currently not understood why certain events descend to the surface while others do not. This study compares a new classification technique of weak vortex events, based on the distribution of potential vorticity, with that of an existing technique and demonstrates that the subdivision of such events into vortex displacements and vortex splits has important implications for tropospheric weather patterns on weekly to monthly time scales. Using reanalysis data it is found that vortex splitting events are correlated with surface weather and lead to positive temperature anomalies over eastern North America of more than 1.5 K, and negative anomalies over Eurasia of up to −3 K. Associated with this is an increase in high-latitude blocking in both the Atlantic and Pacific sectors and a decrease in European blocking. The corresponding signals are weaker during displacement events, although ultimately they are shown to be related to cold-air outbreaks over North America. Because of the importance of stratosphere–troposphere coupling for seasonal climate predictability, identifying the type of stratospheric variability in order to capture the correct surface response will be necessary.
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The Southern Ocean circulation consists of a complicated mixture of processes and phenomena that arise at different time and spatial scales which need to be parametrized in the state-of-the-art climate models. The temporal and spatial scales that give rise to the present-day residual mean circulation are here investigated by calculating the Meridional Overturning Circulation (MOC) in density coordinates from an eddy-permitting global model. The region sensitive to the temporal decomposition is located between 38°S and 63°S, associated with the eddy-induced transport. The ‘‘Bolus’’ component of the residual circulation corresponds to the eddy-induced transport. It is dominated by timescales between 1 month and 1 year. The temporal behavior of the transient eddies is examined in splitting the ‘‘Bolus’’ component into a ‘‘Seasonal’’, an ‘‘Eddy’’ and an ‘‘Inter-monthly’’ component, respectively representing the correlation between density and velocity fluctuations due to the average seasonal cycle, due to mesoscale eddies and due to large-scale motion on timescales longer than one month that is not due to the seasonal cycle. The ‘‘Seasonal’’ bolus cell is important at all latitudes near the surface. The ‘‘Eddy’’ bolus cell is dominant in the thermocline between 50°S and 35°S and over the whole ocean depth at the latitude of the Drake Passage. The ‘‘Inter-monthly’’ bolus cell is important in all density classes and is maximal in the Brazil–Malvinas Confluence and the Agulhas Return Current. The spatial decomposition indicates that a large part of the Eulerian mean circulation is recovered for spatial scales larger than 11.25°, implying that small-scale meanders in the Antarctic Circumpolar Current (ACC), near the Subantarctic and Polar Fronts, and near the Subtropical Front are important in the compensation of the Eulerian mean flow.
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Galactic cosmic rays (GCRs) are modulated by the heliospheric magnetic field (HMF) both over decadal time scales (due to long-term, global HMF variations), and over time scales of a few hours (associated with solar wind structures such as coronal mass ejections or the heliospheric current sheet, HCS). Due to the close association between the HCS, the streamer belt, and the band of slow solar wind, HCS crossings are often associated with corotating interaction regions where fast solar wind catches up and compresses slow solar wind ahead of it. However, not all HCS crossings are associated with strong compressions. In this study we categorize HCS crossings in two ways: Firstly, using the change in magnetic polarity, as either away-to-toward (AT) or toward-to-away (TA) magnetic field directions relative to the Sun and, secondly, using the strength of the associated solar wind compression, determined from the observed plasma density enhancement. For each category, we use superposed epoch analyses to show differences in both solar wind parameters and GCR flux inferred from neutron monitors. For strong-compression HCS crossings, we observe a peak in neutron counts preceding the HCS crossing, followed by a large drop after the crossing, attributable to the so-called ‘snow-plough’ effect. For weak-compression HCS crossings, where magnetic field polarity effects are more readily observable, we instead observe that the neutron counts have a tendency to peak in the away magnetic field sector. By splitting the data by the dominant polarity at each solar polar region, we find that the increase in GCR flux prior to the HCS crossing is primarily from strong compressions in cycles with negative north polar fields due to GCR drift effects. Finally, we report on unexpected differences in GCR behavior between TA weak compressions during opposing polarity cycles.
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An efficient two-level model identification method aiming at maximising a model׳s generalisation capability is proposed for a large class of linear-in-the-parameters models from the observational data. A new elastic net orthogonal forward regression (ENOFR) algorithm is employed at the lower level to carry out simultaneous model selection and elastic net parameter estimation. The two regularisation parameters in the elastic net are optimised using a particle swarm optimisation (PSO) algorithm at the upper level by minimising the leave one out (LOO) mean square error (LOOMSE). There are two elements of original contributions. Firstly an elastic net cost function is defined and applied based on orthogonal decomposition, which facilitates the automatic model structure selection process with no need of using a predetermined error tolerance to terminate the forward selection process. Secondly it is shown that the LOOMSE based on the resultant ENOFR models can be analytically computed without actually splitting the data set, and the associate computation cost is small due to the ENOFR procedure. Consequently a fully automated procedure is achieved without resort to any other validation data set for iterative model evaluation. Illustrative examples are included to demonstrate the effectiveness of the new approaches.
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The effect of the tensor component of the Skyrme effective nucleon-nucleon interaction on the single-particle structure in superheavy elements is studied. A selection of the available Skyrme forces has been chosen and their predictions for the proton and neutron shell closures investigated. The inclusion of the tensor term with realistic coupling strength parameters leads to a small increase in the spin-orbit splitting between the proton 2f7/2 and 2f5/2 partners, opening the Z=114 shell gap over a wide range of nuclei. The Z=126 shell gap, predicted by these models in the absence of the tensor term, is found to be stongly dependent on neutron number with a Z=138 gap opening for large neutron numbers, having a consequent implication for the synthesis of neutron-rich superheavy elements. The predicted neutron shell structures remain largely unchanged by inclusion of the tensor component.
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Background: Coordination of activity between the amygdala and ventromedial prefrontal cortex (vmPFC) is important for fear-extinction learning. Aberrant recruitment of this circuitry is associated with anxiety disorders. Here, we sought to determine if individual differences in future threat uncertainty sensitivity, a potential risk factor for anxiety disorders, underly compromised recruitment of fear extinction circuitry. Twenty-two healthy subjects completed a cued fear conditioning task with acquisition and extinction phases. During the task, pupil dilation, skin conductance response, and functional magnetic resonance imaging were acquired. We assessed the temporality of fear extinction learning by splitting the extinction phase into early and late extinction. Threat uncertainty sensitivity was measured using self-reported intolerance of uncertainty (IU). Results: During early extinction learning, we found low IU scores to be associated with larger skin conductance responses and right amygdala activity to learned threat vs. safety cues, whereas high IU scores were associated with no skin conductance discrimination and greater activity within the right amygdala to previously learned safety cues. In late extinction learning, low IU scores were associated with successful inhibition of previously learned threat, reflected in comparable skin conductance response and right amgydala activity to learned threat vs. safety cues, whilst high IU scores were associated with continued fear expression to learned threat, indexed by larger skin conductance and amygdala activity to threat vs. safety cues. In addition, high IU scores were associated with greater vmPFC activity to threat vs. safety cues in late extinction. Similar patterns of IU and extinction learning were found for pupil dilation. The results were specific for IU and did not generalize to self-reported trait anxiety. Conclusions: Overall, the neural and psychophysiological patterns observed here suggest high IU individuals to disproportionately generalize threat during times of uncertainty, which subsequently compromises fear extinction learning. More broadly, these findings highlight the potential of intolerance of uncertainty-based mechanisms to help understand pathological fear in anxiety disorders and inform potential treatment targets.
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Metal-organic frameworks (MOFs) can be exceptionally good catalytic materials thanks to the presence of active metal centres and a porous structure that is advantageous for molecular adsorption and confinement. We present here a first-principles investigation of the electronic structure of a family of MOFs based on porphyrins connected through phenyl-carboxyl ligands and AlOH species, in order to assess their suitability for the photocatalysis of fuel production reactions using sunlight. We consider structures with protonated porphyrins and those with the protons exchanged with late 3d metal cations (Fe2+, Co2+, Ni2+, Cu2+, Zn2+), a process that we find to be thermodynamically favorable from aqueous solution for all these metals. Our band structure calculations, based on an accurate screened hybrid functional, reveal that the bandgaps are in a favorable range (2.0 to 2.6 eV) for efficient adsorption of solar light. Furthermore, by approximating the vacuum level to the pore center potential, we provide the alignment of the MOFs’ band edges with the redox potentials for water splitting and carbon dioxide reduction, and show that the structures studied here have band edges positions suitable for these reactions at neutral pH.