866 resultados para DENSITY FUNCTIONALS


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We consider evaluating the UK Monetary Policy Committee's inflation density forecasts using probability integral transform goodness-of-fit tests. These tests evaluate the whole forecast density. We also consider whether the probabilities assigned to inflation being in certain ranges are well calibrated, where the ranges are chosen to be those of particular relevance to the MPC, given its remit of maintaining inflation rates in a band around per annum. Finally, we discuss the decision-based approach to forecast evaluation in relation to the MPC forecasts

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The concentration of high density lipoprotein-cholesterol (HDL-C) has been found consistently to be a powerful negative predictor of premature coronary heart disease (CHD) in human prospective population studies. There is also circumstantial evidence from human intervention studies and direct evidence from animal intervention studies that HDLs protect against the development of atherosclerosis. HDLs have several documented functions, although the precise mechanism by which they prevent atherosclerosis remains uncertain. Nor is it known whether the cardioprotective properties of HDL are specific to one or more of the many HDL subpopulations that comprise the HDL fraction in human plasma. Several lifestyle and pharmacological interventions have the capacity to raise the level of HDL-C, although it is not known whether all are equally protective. Indeed, despite the large body of information identifying HDLs as potential therapeutic targets for the prevention of atherosclerosis, there remain many unanswered questions that must be addressed as a matter of urgency before embarking wholesale on HDL-C-raising therapies as strategies to prevent CHD. This review summarises what is known and highlights what we still need to know.

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The role of low-density lipoprotein in the development of coronary heart disease (CHD) is well recognised. There is also growing evidence that high-density lipoprotein cholesterol (HDL-C) is a powerful inverse predictor for premature CHD and that maintaining a high HDL-C level may guard against atherosclerosis. Patients with low HDL-C levels often also have central obesity, insulin resistance and other features of the metabolic syndrome. This syndrome is both increasingly common and strongly implicated in the growing worldwide epidemic of type 2 diabetes. HDL-C may be increased by lifestyle changes, e.g. weight loss, physical activity and smoking cessation. Pharmacological agents such as fibrates, niacin and statins have also been shown significantly to elevate HDL-C. Although current guidelines are beginning to recognise the protective role of HDL-C level in preventing coronary events, HDL-C should be adopted soon as a target for intervention in its own right.

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We explore the large spatial variation in the relationship between population density and burned area, using continental-scale Geographically Weighted Regression (GWR) based on 13 years of satellite-derived burned area maps from the global fire emissions database (GFED) and the human population density from the gridded population of the world (GPW 2005). Significant relationships are observed over 51.5% of the global land area, and the area affected varies from continent to continent: population density has a significant impact on fire over most of Asia and Africa but is important in explaining fire over < 22% of Europe and Australia. Increasing population density is associated with both increased and decreased in fire. The nature of the relationship depends on land-use: increasing population density is associated with increased burned are in rangelands but with decreased burned area in croplands. Overall, the relationship between population density and burned area is non-monotonic: burned area initially increases with population density and then decreases when population density exceeds a threshold. These thresholds vary regionally. Our study contributes to improved understanding of how human activities relate to burned area, and should contribute to a better estimate of atmospheric emissions from biomass burning.

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We present the results of a density functional theory (DFT) investigation of the surfaces of rutile-like vanadium dioxide, VO2(R). We calculate the surface energies of low Miller index planes, and find that the most stable surface orientation is the (110). The equilibrium morphology of a VO2(R) particle has an acicular shape, laterally confined by (110) planes and topped by (011) planes. The redox properties of the (110) surface are investigated by calculating the relative surface free energies of the non-stoichiometric compositions as a function of oxygen chemical potential. It is found that the VO2(110) surface is oxidized with respect to the stoichiometric composition, not only at ambient conditions but also at the more reducing conditions under which bulk VO2 is stable in comparison with bulk V2O5. The adsorbed oxygen forms surface vanadyl species much more favorably than surface peroxo species.

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This paper introduces a new adaptive nonlinear equalizer relying on a radial basis function (RBF) model, which is designed based on the minimum bit error rate (MBER) criterion, in the system setting of the intersymbol interference channel plus a co-channel interference. Our proposed algorithm is referred to as the on-line mixture of Gaussians estimator aided MBER (OMG-MBER) equalizer. Specifically, a mixture of Gaussians based probability density function (PDF) estimator is used to model the PDF of the decision variable, for which a novel on-line PDF update algorithm is derived to track the incoming data. With the aid of this novel on-line mixture of Gaussians based sample-by-sample updated PDF estimator, our adaptive nonlinear equalizer is capable of updating its equalizer’s parameters sample by sample to aim directly at minimizing the RBF nonlinear equalizer’s achievable bit error rate (BER). The proposed OMG-MBER equalizer significantly outperforms the existing on-line nonlinear MBER equalizer, known as the least bit error rate equalizer, in terms of both the convergence speed and the achievable BER, as is confirmed in our simulation study

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Polymers with the ability to heal themselves could provide access to materials with extended lifetimes in a wide range of applications such as surface coatings, automotive components and aerospace composites. Here we describe the synthesis and characterisation of two novel, stimuli-responsive, supramolecular polymer blends based on π-electron-rich pyrenyl residues and π-electron-deficient, chain-folding aromatic diimides that interact through complementary π–π stacking interactions. Different degrees of supramolecular “cross-linking” were achieved by use of divalent or trivalent poly(ethylene glycol)-based polymers featuring pyrenyl end-groups, blended with a known diimide–ether copolymer. The mechanical properties of the resulting polymer blends revealed that higher degrees of supramolecular “cross-link density” yield materials with enhanced mechanical properties, such as increased tensile modulus, modulus of toughness, elasticity and yield point. After a number of break/heal cycles, these materials were found to retain the characteristics of the pristine polymer blend, and this new approach thus offers a simple route to mechanically robust yet healable materials.

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This paper investigates urban canopy layers (UCL) ventilation under neutral atmospheric condition with the same building area density (λp=0.25) and frontal area density (λf=0.25) but various urban sizes, building height variations, overall urban forms and wind directions. Turbulent airflows are first predicted by CFD simulations with standard k-ε model evaluated by wind tunnel data. Then air change rates per hour (ACH) and canopy purging flow rate (PFR) are numerically analyzed to quantify the rate of air exchange and the net ventilation capacity induced by mean flows and turbulence. With a parallel approaching wind (θ=0o), the velocity ratio first decreases in the adjustment region, followed by the fully-developed region where the flow reaches a balance. Although the flow quantities macroscopically keep constant, however ACH decreases and overall UCL ventilation becomes worse if urban size rises from 390m to 5km. Theoretically if urban size is infinite, ACH may reach a minimum value depending on local roof ventilation, and it rises from 1.7 to 7.5 if the standard deviation of building height variations increases (0% to 83.3%). Overall UCL ventilation capacity (PFR) with a square overall urban form (Lx=Ly=390m) is better as θ=0o than oblique winds (θ=15o, 30o, 45o), and it exceeds that of a staggered urban form under all wind directions (θ=0o to 45o), but is less than that of a rectangular urban form (Lx=570m, Ly=270m) under most wind directions (θ=30o to 90o). Further investigations are still required to quantify the net ventilation efficiency induced by mean flows and turbulence.

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Pollinator declines have raised concerns about the persistence of plant species that depend on insect pollination, in particular by bees, for their reproduction. The impact of pollinator declines remains unknown for species-rich plant communities found in temperate seminatural grasslands. We investigated effects of land-use intensity in the surrounding landscape on the distribution of plant traits related to insect pollination in 239 European seminatural grasslands. Increasing arable land use in the surrounding landscape consistently reduced the density of plants depending on bee and insect pollination. Similarly, the relative abundance of bee-pollination-dependent plants increased with higher proportions of non-arable agricultural land (e.g. permanent grassland). This was paralleled by an overall increase in bee abundance and diversity. By isolating the impact of the surrounding landscape from effects of local habitat quality, we show for the first time that grassland plants dependent on insect pollination are particularly susceptible to increasing land-use intensity in the landscape.

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The relationship between food security and sustainable land use is considered to be of the uttermost importance to increase yields without having to increase the agricultural land area over which crops are grown. In the present study nitrogen concentration (25 and 85 kg ha-1) and planting density (6.7, 10 and 25 plants m-2) were investigated for their effect on whole plant physiology and pod seed yield in kale (Brassica oleracea), to determine if the fruit (pod) yield could be manipulated agronomically. Nitrogen concentration did not significantly affect seed yield and it is therefore recommended that the lower concentration be used commercially. Conversely planting density did have a significant effect with increases in seed yield observed at the highest planting density of 25 plants m-2, therefore this high planting density would be recommended commercially to maximise area efficiency, highlighting that simple agronomic changes are capable of increasing crop yields over a set area.

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These findings strongly suggest that CFPE do not generally result from increased bacterial density within the airways. Instead, data presented here are consistent with alternative models of pulmonary exacerbation.

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It is widely thought that changes in both the surface buoyancy fluxes and wind stress drive variability in the Atlantic meridional overturning circulation (AMOC), but that they drive variability on different time scales. For example, wind forcing dominates short-term variability through its effects on Ekman currents and coastal upwelling, whereas buoyancy forcing is important for longer time scales (multiannual and decadal). However, the role of the wind forcing on multiannual to decadal time scales is less clear. Here the authors present an analysis of simulations with the Nucleus for European Modelling of the Ocean (NEMO) ocean model with the aim of explaining the important drivers of the zonal density gradient at 26°N, which is directly related to the AMOC. In the experiments, only one of either the wind stress or the buoyancy forcing is allowed to vary in time, whereas the other remains at its seasonally varying climatology. On subannual time scales, variations in the density gradient, and in the AMOC minus Ekman, are driven largely by local wind-forced coastal upwelling at both the western and eastern boundaries. On decadal time scales, buoyancy forcing related to the North Atlantic Oscillation dominates variability in the AMOC. Interestingly, however, it is found that wind forcing also plays a role at longer time scales, primarily impacting the interannual variability through the excitation of Rossby waves in the central Atlantic, which propagate westward to interact with the western boundary, but also by modulating the decadal time-scale response to buoyancy forcing.

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Understanding the interaction of organic molecules with TiO2 surfaces is important for a wide range of technological applications. While density functional theory (DFT) calculations can provide valuable insight about these interactions, traditional DFT approaches with local exchange-correlation functionals suffer from a poor description of non-bonding van der Waals (vdW) interactions. We examine here the contribution of vdW forces to the interaction of small organic molecules (methane, methanol, formic acid and glycine) with the TiO2 (110) surface, based on DFT calculations with the optB88-vdW functional. The adsorption geometries and energies at different configurations were also obtained in the standard generalized gradient approximation (GGA-PBE) for comparison. We find that the optB88-vdW consistently gives shorter surface adsorbate-to-surface distances and slightly stronger interactions than PBE for the weak (physisorbed) modes of adsorption. In the case of strongly adsorbed (chemisorbed) molecules both functionals give similar results for the adsorption geometries, and also similar values of the relative energies between different chemisorption modes for each molecule. In particular both functionals predict that dissociative adsorption is more favourable than molecular adsorption for methanol, formic acid and glycine, in general agreement with experiment. The dissociation energies obtained from both functionals are also very similar, indicating that vdW interactions do not affect the thermodynamics of surface deprotonation. However, the optB88-vdW always predicts stronger adsorption than PBE. The comparison of the methanol adsorption energies with values obtained from a Redhead analysis of temperature programmed desorption data suggests that optB88-vdW significantly overestimates the adsorption strength, although we warn about the uncertainties involved in such comparisons.

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The incorporation of cobalt in mixed metal carbonates is a possible route to the immobilization of this toxic element in the environment. However, the thermodynamics of (Ca,Co)CO3 solid solutions are still unclear due to conflicting data from experiment and from the observation of natural ocurrences. We report here the results of a computer simulation study of the mixing of calcite (CaCO3) and spherocobaltite (CoCO3), using density functional theory calculations. Our simulations suggest that previously proposed thermodynamic models, based only on the range of observed compositions, significantly overestimate the solubility between the two solids and therefore underestimate the extension of the miscibility gap under ambient conditions. The enthalpy of mixing of the disordered solid solution is strongly positive and moderately asymmetric: calcium incorporation in spherocobaltite is more endothermic than cobalt incorporation in calcite. Ordering of the impurities in (0001) layers is energetically favourable with respect to the disordered solid solution at low temperatures and intermediate compositions, but the ordered phase is still unstable to demixing. We calculate the solvus and spinodal lines in the phase diagram using a sub-regular solution model, and conclude that many Ca1-xCoxCO3 mineral solid solutions (with observed compositions of up to x=0.027, and above x=0.93) are metastable with respect to phase separation. We also calculate solid/aqueous distribution coefficients to evaluate the effect of the strong non-ideality of mixing on the equilibrium with aqueous solution, showing that the thermodynamically-driven incorporation of cobalt in calcite (and of calcium in spherocobaltite) is always very low, regardless of the Co/Ca ratio of the aqueous environment.

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The performance of rank dependent preference functionals under risk is comprehensively evaluated using Bayesian model averaging. Model comparisons are made at three levels of heterogeneity plus three ways of linking deterministic and stochastic models: the differences in utilities, the differences in certainty equivalents and contextualutility. Overall, the"bestmodel", which is conditional on the form of heterogeneity is a form of Rank Dependent Utility or Prospect Theory that cap tures the majority of behaviour at both the representative agent and individual level. However, the curvature of the probability weighting function for many individuals is S-shaped, or ostensibly concave or convex rather than the inverse S-shape commonly employed. Also contextual utility is broadly supported across all levels of heterogeneity. Finally, the Priority Heuristic model, previously examined within a deterministic setting, is estimated within a stochastic framework, and allowing for endogenous thresholds does improve model performance although it does not compete well with the other specications considered.