943 resultados para electron correlations


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The issue of whether Real Estate Investment Trusts (REITs) should pursue a focused or diversified investment strategy remains an ongoing debate within both the academic and industry communities. This article considers the relationship between REITs focused on different property sectors in a Generalized Autoregressive Conditional Heteroscedasticity-Dynamic Control Correlation (GARCH-DCC) framework. The daily conditional correlations reveal that since 1990 there has been a marked upward trend in the coefficients between US REIT sub-sectors. The findings imply that REITs are behaving in a far more homogeneous manner than in the past. Furthermore, the argument that REITs should be focused in order that investors can make the diversification decision is reduced.

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It is shown here that the angular relation equations between direct and reciprocal vectors are very similar to the angular relation equations in Euler's theorem. These two sets of equations are usually treated separately as unrelated equations in different fields. In this careful study, the connection between the two sets of angular equations is revealed by considering the cosine rule for the spherical triangle. It is found that understanding of the correlation is hindered by the facts that the same variables are defined differently and different symbols are used to represent them in the two fields. Understanding the connection between different concepts is not only stimulating and beneficial, but also a fundamental tool in innovation and research, and has historical significance. The background of the work presented here contains elements of many scientific disciplines. This work illustrates the common ground of two theories usually considered separately and is therefore of benefit not only for its own sake but also to illustrate a general principle that a theory relevant to one discipline can often be used in another. The paper works with chemistry related concepts using mathematical methodologies unfamiliar to the usual audience of mainstream experimental and theoretical chemists.

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Total ozone trends are typically studied using linear regression models that assume a first-order autoregression of the residuals [so-called AR(1) models]. We consider total ozone time series over 60°S–60°N from 1979 to 2005 and show that most latitude bands exhibit long-range correlated (LRC) behavior, meaning that ozone autocorrelation functions decay by a power law rather than exponentially as in AR(1). At such latitudes the uncertainties of total ozone trends are greater than those obtained from AR(1) models and the expected time required to detect ozone recovery correspondingly longer. We find no evidence of LRC behavior in southern middle-and high-subpolar latitudes (45°–60°S), where the long-term ozone decline attributable to anthropogenic chlorine is the greatest. We thus confirm an earlier prediction based on an AR(1) analysis that this region (especially the highest latitudes, and especially the South Atlantic) is the optimal location for the detection of ozone recovery, with a statistically significant ozone increase attributable to chlorine likely to be detectable by the end of the next decade. In northern middle and high latitudes, on the other hand, there is clear evidence of LRC behavior. This increases the uncertainties on the long-term trend attributable to anthropogenic chlorine by about a factor of 1.5 and lengthens the expected time to detect ozone recovery by a similar amount (from ∼2030 to ∼2045). If the long-term changes in ozone are instead fit by a piecewise-linear trend rather than by stratospheric chlorine loading, then the strong decrease of northern middle- and high-latitude ozone during the first half of the 1990s and its subsequent increase in the second half of the 1990s projects more strongly on the trend and makes a smaller contribution to the noise. This both increases the trend and weakens the LRC behavior at these latitudes, to the extent that ozone recovery (according to this model, and in the sense of a statistically significant ozone increase) is already on the verge of being detected. The implications of this rather controversial interpretation are discussed.

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Our knowledge of stratospheric O3-N2O correlations is extended, and their potential for model-measurement comparison assessed, using data from the Atmospheric Chemistry Experiment (ACE) satellite and the Canadian Middle Atmosphere Model (CMAM). ACE provides the first comprehensive data set for the investigation of interhemispheric, interseasonal, and height-resolved differences of the O_3-N_2O correlation structure. By subsampling the CMAM data, the representativeness of the ACE data is evaluated. In the middle stratosphere, where the correlations are not compact and therefore mainly reflect the data sampling, joint probability density functions provide a detailed picture of key aspects of transport and mixing, but also trace polar ozone loss. CMAM captures these important features, but exhibits a displacement of the tropical pipe into the Southern Hemisphere (SH). Below about 21 km, the ACE data generally confirm the compactness of the correlations, although chemical ozone loss tends to destroy the compactness during late winter/spring, especially in the SH. This allows a quantitative comparison of the correlation slopes in the lower and lowermost stratosphere (LMS), which exhibit distinct seasonal cycles that reveal the different balances between diabatic descent and horizontal mixing in these two regions in the Northern Hemisphere (NH), reconciling differences found in aircraft measurements, and the strong role of chemical ozone loss in the SH. The seasonal cycles are qualitatively well reproduced by CMAM, although their amplitude is too weak in the NH LMS. The correlation slopes allow a "chemical" definition of the LMS, which is found to vary substantially in vertical extent with season.

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Correlations between various chemical species simulated by the Canadian Middle Atmosphere Model, a general circulation model with fully interactive chemistry, are considered in order to investigate the general conditions under which compact correlations can be expected to form. At the same time, the analysis serves to validate the model. The results are compared to previous work on this subject, both from theoretical studies and from atmospheric measurements made from space and from aircraft. The results highlight the importance of having a data set with good spatial coverage when working with correlations and provide a background against which the compactness of correlations obtained from atmospheric measurements can be confirmed. It is shown that for long-lived species, distinct correlations are found in the model in the tropics, the extratropics, and the Antarctic winter vortex. Under these conditions, sparse sampling such as arises from occultation instruments is nevertheless suitable to define a chemical correlation within each region even from a single day of measurements, provided a sufficient range of mixing ratio values is sampled. In practice, this means a large vertical extent, though the requirements are less stringent at more poleward latitudes.

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The structures of 2-hydroxybenzamide(C7H7NO2) and 2-methoxybenzamide (C8H9NO2) have been determined in the gas-phase by electron diffraction using results from quantum chemical calculations to inform restraints used on the structural parameters. Theoretical methods (HF and MP2/6-311+G(d,p)) predict four stable conformers for both 2-hydroxybenzamide and 2-methoxybenzamide. For both compounds, evidence for intramolecular hydrogen bonding is presented. In 2-hydroxybenzamide, the observed hydrogen bonded fragment is between the hydroxyl and carbonyl groups, while in 2-methoxybenzamide, the hydrogen bonded fragment is between one of the hydrogen atoms of the amide group and the methoxy oxygen atom.

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In order to make best use of the opportunities provided by space missions such as the Radiation Belt Storm Probes, we determine the response of complementary subionospheric radiowave propagation measurements (VLF), riometer absorption measurements (CNA), and GPS-produced total electron content (vTEC) to different energetic electron precipitation (EEP). We model the relative sensitivity and responses of these instruments to idealised monoenergetic beams of precipitating electrons, and more realistic EEP spectra chosen to represent radiation belts and substorm precipitation. In the monoenergetic beam case, we find riometers are more sensitive to the same EEP event occurring during the day than during the night, while subionospheric VLF shows the opposite relationship, and the change in vTEC is independent. In general, the subionospheric VLF measurements are much more sensitive than the other two techniques for EEP over 200 keV, responding to flux magnitudes two-three orders of magnitude smaller than detectable by a riometer. Detectable TEC changes only occur for extreme monoenergetic fluxes. For the radiation belt EEP case, clearly detectable subionospheric VLF responses are produced by daytime fluxes that are ~10 times lower than required for riometers, while nighttime fluxes can be 10,000 times lower. Riometers are likely to respond only to radiation belt fluxes during the largest EEP events and vTEC is unlikely to be significantly disturbed by radiation belt EEP. For the substorm EEP case both the riometer absorption and the subionospheric VLF technique respond significantly, as does the change in vTEC, which is likely to be detectable at ~3-4 TECu.

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Using a self-consistent drift-kinetic simulation code, we investigate whether electron acceleration owing to shear Alfvén waves in the plasma sheet boundary layer is sufficient to cause auroral brightening in the ionosphere. The free parameters used in the simulation code are guided by in situ observations of wave and plasma parameters in the magnetosphere at distances >4 RE from the Earth. For the perpendicular wavelength used in the study, which maps to ∼4 km at 110 km altitude, there is a clear amplitude threshold which determines whether magnetospheric shear Alfvén waves above the classical auroral acceleration region can excite sufficient electrons to create the aurora. Previous studies reported wave amplitudes that easily exceed this threshold; hence, the results reported in this paper demonstrate that auroral acceleration owing to shear Alfvén waves can occur in the magnetosphere at distances >4 RE from the Earth.

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Results from 1D Vlasov drift-kinetic plasma simulations reveal how and where auroral electrons are accelerated along Earth’s geomagnetic field. In the warm plasma sheet, electrons become trapped in shear Alfven waves, preventing immediate wave damping. As waves move to regions with larger vTe=vA, their parallel electric field decreases, and the trapped electrons escape their influence. The resulting electron distribution functions compare favorably with in situ observations, demonstrating for the first time a self-consistent link between Alfven waves and electrons that form aurora.

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The optimal utilisation of hyper-spectral satellite observations in numerical weather prediction is often inhibited by incorrectly assuming independent interchannel observation errors. However, in order to represent these observation-error covariance structures, an accurate knowledge of the true variances and correlations is needed. This structure is likely to vary with observation type and assimilation system. The work in this article presents the initial results for the estimation of IASI interchannel observation-error correlations when the data are processed in the Met Office one-dimensional (1D-Var) and four-dimensional (4D-Var) variational assimilation systems. The method used to calculate the observation errors is a post-analysis diagnostic which utilises the background and analysis departures from the two systems. The results show significant differences in the source and structure of the observation errors when processed in the two different assimilation systems, but also highlight some common features. When the observations are processed in 1D-Var, the diagnosed error variances are approximately half the size of the error variances used in the current operational system and are very close in size to the instrument noise, suggesting that this is the main source of error. The errors contain no consistent correlations, with the exception of a handful of spectrally close channels. When the observations are processed in 4D-Var, we again find that the observation errors are being overestimated operationally, but the overestimation is significantly larger for many channels. In contrast to 1D-Var, the diagnosed error variances are often larger than the instrument noise in 4D-Var. It is postulated that horizontal errors of representation, not seen in 1D-Var, are a significant contributor to the overall error here. Finally, observation errors diagnosed from 4D-Var are found to contain strong, consistent correlation structures for channels sensitive to water vapour and surface properties.

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This paper proposes two new tests for linear and nonlinear lead/lag relationships between time series based on the concepts of cross-correlations and cross-bicorrelations, respectively. The tests are then applied to a set of Sterling-denominated exchange rates. Our analysis indicates that there existed periods during the post-Bretton Woods era where the temporal relationship between different exchange rates was strong, although these periods have become less frequent over the past 20 years. In particular, our results demonstrate the episodic nature of the nonlinearity, and have implications for the speed of flow of information between financial series. The method generalises recently proposed tests for nonlinearity to the multivariate context.

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We investigate electron acceleration due to shear Alfven waves in a collissionless plasma for plasma parameters typical of 4–5RE radial distance from the Earth along auroral field lines. Recent observational work has motivated this study, which explores the plasma regime where the thermal velocity of the electrons is similar to the Alfven speed of the plasma, encouraging Landau resonance for electrons in the wave fields. We use a self-consistent kinetic simulation model to follow the evolution of the electrons as they interact with a short-duration wave pulse, which allows us to determine the parallel electric field of the shear Alfven wave due to both electron inertia and electron pressure effects. The simulation demonstrates that electrons can be accelerated to keV energies in a modest amplitude sub-second period wave. We compare the parallel electric field obtained from the simulation with those provided by fluid approximations.

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A pyridyl-functionalized diiron dithiolate complex, [μ-(4-pyCH2−NMI-S2)Fe2(CO)6] (3, py = pyridine(ligand), NMI = naphthalene monoimide) was synthesized and fully characterized. In the presence of zinc tetraphenylporphyrin (ZnTPP), a self-assembled 3·ZnTPP complex was readily formed in CH2Cl2 by the coordination of the pyridyl nitrogen to the porphyrin zinc center. Ultrafast photoinduced electron transfer from excited ZnTPP to complex 3 in the supramolecular assembly was observed in real time by monitoring the ν(CO) and ν(CO)NMI spectral changes with femtosecond time-resolved infrared (TRIR) spectroscopy. We have confirmed that photoinduced charge separation produced the monoreduced species by comparing the time-resolved IR spectra with the conventional IR spectra of 3•− generated by reversible electrochemical reduction. The lifetimes for the charge separation and charge recombination processes were found to be τCS = 40 ± 3 ps and τCR = 205 ± 14 ps, respectively. The charge recombination is much slower than that in an analogous covalent complex, demonstrating the potential of a supramolecular approach to extend the lifetime of the chargeseparated state in photocatalytic complexes. The observed vibrational frequency shifts provide a very sensitive probe of the delocalization of the electron-spin density over the different parts of the Fe2S2 complex. The TR and spectro-electrochemical IR spectra, electron paramagnetic resonance spectra, and density functional theory calculations all show that the spin density in 3•− is delocalized over the diiron core and the NMI bridge. This delocalization explains why the complex exhibits low catalytic dihydrogen production even though it features a very efficient photoinduced electron transfer. The ultrafast porphyrin-to-NMIS2−Fe2(CO)6 photoinduced electron transfer is the first reported example of a supramolecular Fe2S2-hydrogenase model studied by femtosecond TRIR spectroscopy. Our results show that TRIR spectroscopy is a powerful tool to investigate photoinduced electron transfer in potential dihydrogen-producing catalytic complexes, and that way to optimize their performance by rational approaches.

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Protons and electrons are being exploited in different natural charge transfer processes. Both types of charge carriers could be, therefore, responsible for charge transport in biomimetic self-assembled peptide nanostructures. The relative contribution of each type of charge carrier is studied in the present work for fi brils self-assembled from amyloid- β derived peptide molecules, in which two non-natural thiophene-based amino acids are included. It is shown that under low humidity conditions both electrons and protons contribute to the conduction, with current ratio of 1:2 respectively, while at higher relative humidity proton transport dominates the conductance. This hybrid conduction behavior leads to a bimodal exponential dependence of the conductance on the relative humidity. Furthermore, in both cases the conductance is shown to be affected by the peptide folding state under the entire relative humidity range. This unique hybrid conductivity behavior makes self-assembled peptide nanostructures powerful building blocks for the construction of electric devices that could use either or both types of charge carriers for their function.