891 resultados para Log ESEO, GPS, orbite, pseudorange, least square


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The new square-planar Ni-II-N2O2 complex [Ni(L-Me)] (1(Me)), where L-Me, stands for the dianionic phenolato form of N,N'bis(3,5-di-tert-butyl-salicylidene)-4,5-dimethyl-1,2-phenyl- enediamine ((LH2)-L-Me), has been synthesised and fully characterised. X-ray crystallography was also used for the characterisation. The electrochemical one-electron oxidation of 1(Me) produces the thermally stable (within the temperature range 10-295 K) cationic species (1(Me))(+). The UV/Vis and X-band EPR experimental data, supported by DFT calculations, indicate that (1(Me))(+), is best described as a Ni-II monoradical complex and, thus, does NOT exist in a Ni-III ground state, in contrast to its demethylated counterpart [Ni(L-H)](+) (1(H))(+) below 170 K.

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A large number of urban surface energy balance models now exist with different assumptions about the important features of the surface and exchange processes that need to be incorporated. To date, no com- parison of these models has been conducted; in contrast, models for natural surfaces have been compared extensively as part of the Project for Intercomparison of Land-surface Parameterization Schemes. Here, the methods and first results from an extensive international comparison of 33 models are presented. The aim of the comparison overall is to understand the complexity required to model energy and water exchanges in urban areas. The degree of complexity included in the models is outlined and impacts on model performance are discussed. During the comparison there have been significant developments in the models with resulting improvements in performance (root-mean-square error falling by up to two-thirds). Evaluation is based on a dataset containing net all-wave radiation, sensible heat, and latent heat flux observations for an industrial area in Vancouver, British Columbia, Canada. The aim of the comparison is twofold: to identify those modeling ap- proaches that minimize the errors in the simulated fluxes of the urban energy balance and to determine the degree of model complexity required for accurate simulations. There is evidence that some classes of models perform better for individual fluxes but no model performs best or worst for all fluxes. In general, the simpler models perform as well as the more complex models based on all statistical measures. Generally the schemes have best overall capability to model net all-wave radiation and least capability to model latent heat flux.

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Rh-I-terpyridine complexes have been unambiguously formed for the first time. The 2,21:6',2"-terpyridine (tpy), 4'-chloro-2,2':6',2"-terpyridine (4'-Cl-tpy) and 4'-(tert-butyldimethylsilyl-ortho-carboranyl)-2,2':6',2"-terpyridine (carboranyl-tpy) ligands were used for successful syntheses and characterisation of the corresponding Rh-I complexes with halide coligands, [Rh(X)(4'-Y-terpyridine)] (X = Cl, Y = H, Cl, carboranyl; X = Br, Y = H). All four neutral Rh-tpy complexes are square planar, with Rh-X bonds in the plane of the 4'-Y-terpyridine ligands. Full characterisation of these dark blue, highly air-sensitive compounds was hampered by their poor solubility in various organic solvents. This is mainly due to the formation of pi-stacked aggregates, as evidenced by the crystal structure of [Rh(Cl)(tpy)]; in addition, [Rh(Cl)(carboranyl-tpy)] merely forms discrete dimers. The (bonding) properties of the novel Rh-I-terpyridine complexes have been studied with single-crystal X-ray diffraction, (time-dependent) density functional theoretical (DFT) calculations, far-infrared spectroscopy, electronic absorption spectroscopy and cyclic voltammetry. From DFT calculations, the HOMO of the studied Rh-I-terpyridine complexes involves predominantly the metal centre, while the LUMO resides on the terpyridine ligand. Absorption bands of the studied complexes in the visible region (400-900 nm) can be assigned to MLCT and MLCT/XLCT transitions. The relatively low oxidation potentials of [Rh(X)(tpy)] (X = Cl, Br) point to a high electron density on the metal centre. This makes the Rh-I-terpyridine complexes strongly nucleophilic and (potentially) highly reactive towards various (small) substrate molecules containing carbon-halide bonds.

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Time-resolved kinetic studies of silylene, SiH2, generated by laser flash photolysis of phenylsilane, have been carried out to obtain rate constants for its bimolecular reactions with oxirane, oxetane, and tetrahydrofuran (THF). The reactions were studied in the gas phase over the pressure range 1-100 Torr in SF6 bath gas, at four or five temperatures in the range 294-605 K. All three reactions showed pressure dependences characteristic of third-body-assisted association reactions with, surprisingly, SiH2 + oxirane showing the least and SiH2 + THF showing the most pressure dependence. The second-order rate constants obtained by extrapolation to the high-pressure limits at each temperature fitted the Arrhenius equations where the error limits are single standard deviations: log(k(oxirane)(infinity)/cm(3) molecule(-1) s(-1)) = (-11.03 +/- 0.07) + (5.70 +/- 0.51) kJ mol(-1)/RT In 10 log(k(oxetane)(infinity)/cm(3) molecule(-1) s(-1)) = (-11.17 +/- 0.11) + (9.04 +/- 0.78) kJ mol(-1)/RT In 10 log(k(THF)(infinity)/cm(3) molecule(-1) s(-1)) = (-10.59 +/- 0.10) + (5.76 +/- 0.65) kJ mol(-1)/RT In 10 Binding-energy values of 77, 97, and 92 kJ mol(-1) have been obtained for the donor-acceptor complexes of SiH2 with oxirane, oxetane, and THF, respectively, by means of quantum chemical (ab initio) calculations carried Out at the G3 level. The use of these values to model the pressure dependences of these reactions, via RRKM theory, provided a good fit only in the case of SiH2 + THF. The lack of fit in the other two cases is attributed to further reaction pathways for the association complexes of SiH2 with oxirane and oxetane. The finding of ethene as a product of the SiH2 + oxirane reaction supports a pathway leading to H2Si=O + C2H4 predicted by the theoretical calculations of Apeloig and Sklenak.

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The recursive least-squares algorithm with a forgetting factor has been extensively applied and studied for the on-line parameter estimation of linear dynamic systems. This paper explores the use of genetic algorithms to improve the performance of the recursive least-squares algorithm in the parameter estimation of time-varying systems. Simulation results show that the hybrid recursive algorithm (GARLS), combining recursive least-squares with genetic algorithms, can achieve better results than the standard recursive least-squares algorithm using only a forgetting factor.

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A self-tuning proportional, integral and derivative control scheme based on genetic algorithms (GAs) is proposed and applied to the control of a real industrial plant. This paper explores the improvement in the parameter estimator, which is an essential part of an adaptive controller, through the hybridization of recursive least-squares algorithms by making use of GAs and the possibility of the application of GAs to the control of industrial processes. Both the simulation results and the experiments on a real plant show that the proposed scheme can be applied effectively.

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A novel partitioned least squares (PLS) algorithm is presented, in which estimates from several simple system models are combined by means of a Bayesian methodology of pooling partial knowledge. The method has the added advantage that, when the simple models are of a similar structure, it lends itself directly to parallel processing procedures, thereby speeding up the entire parameter estimation process by several factors.

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A very efficient learning algorithm for model subset selection is introduced based on a new composite cost function that simultaneously optimizes the model approximation ability and model adequacy. The derived model parameters are estimated via forward orthogonal least squares, but the subset selection cost function includes an A-optimality design criterion to minimize the variance of the parameter estimates that ensures the adequacy and parsimony of the final model. An illustrative example is included to demonstrate the effectiveness of the new approach.

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Emergency vehicles use high-amplitude sirens to warn pedestrians and other road users of their presence. Unfortunately, the siren noise enters the vehicle and corrupts the intelligibility of two-way radio voice com-munications from the emergency vehicle to a control room. Often the siren has to be turned off to enable the control room to hear what is being said which subsequently endangers people's lives. A digital signal processing (DSP) based system for the cancellation of siren noise embedded within speech is presented. The system has been tested with the least mean square (LMS), normalised least mean square (NLMS) and affine projection algorithm (APA) using recordings from three common types of sirens (two-tone, wail and yelp) from actual test vehicles. It was found that the APA with a projection order of 2 gives comparably improved cancellation over the LMS and NLMS with only a moderate increase in algorithm complexity and code size. Therefore, this siren noise cancellation system using the APA offers an improvement in cancellation achieved by previous systems. The removal of the siren noise improves the response time for the emergency vehicle and thus the system can contribute to saving lives. The system also allows voice communication to take place even when the siren is on and as such the vehicle offers less risk of danger when moving at high speeds in heavy traffic.

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This paper investigates the robustness of a hybrid analog/digital feedback active noise cancellation (ANC) headset system. The digital ANC systems with the filtered-x least-mean-square (FXLMS) algorithm require accurate estimation of the secondary path for the stability and convergence of the algorithm. This demands a great challenge for the ANC headset design because the secondary path may fluctuate dramatically such as when the user adjusts the position of the ear-cup. In this paper, we analytically show that adding an analog feedback loop into the digital ANC systems can effectively reduce the plant fluctuation, thus achieving a more robust system. The method for designing the analog controller is highlighted. A practical hybrid analog/digital feedback ANC headset has been built and used to conduct experiments, and the experimental results show that the hybrid headset system is more robust under large plant fluctuation, and has achieved satisfactory noise cancellation for both narrowband and broadband noises.

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This paper analyzes the convergence behavior of the least mean square (LMS) filter when used in an adaptive code division multiple access (CDMA) detector consisting of a tapped delay line with adjustable tap weights. The sampling rate may be equal to or higher than the chip rate, and these correspond to chip-spaced (CS) and fractionally spaced (FS) detection, respectively. It is shown that CS and FS detectors with the same time-span exhibit identical convergence behavior if the baseband received signal is strictly bandlimited to half the chip rate. Even in the practical case when this condition is not met, deviations from this observation are imperceptible unless the initial tap-weight vector gives an extremely large mean squared error (MSE). This phenomenon is carefully explained with reference to the eigenvalues of the correlation matrix when the input signal is not perfectly bandlimited. The inadequacy of the eigenvalue spread of the tap-input correlation matrix as an indicator of the transient behavior and the influence of the initial tap weight vector on convergence speed are highlighted. Specifically, a initialization within the signal subspace or to the origin leads to very much faster convergence compared with initialization in the a noise subspace.

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Adaptive filters used in code division multiple access (CDMA) receivers to counter interference have been formulated both with and without the assumption of training symbols being transmitted. They are known as training-based and blind detectors respectively. We show that the convergence behaviour of the blind minimum-output-energy (MOE) detector can be quite easily derived, unlike what was implied by the procedure outlined in a previous paper. The simplification results from the observation that the correlation matrix determining convergence performance can be made symmetric, after which many standard results from the literature on least mean square (LMS) filters apply immediately.

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Adaptive least mean square (LMS) filters with or without training sequences, which are known as training-based and blind detectors respectively, have been formulated to counter interference in CDMA systems. The convergence characteristics of these two LMS detectors are analyzed and compared in this paper. We show that the blind detector is superior to the training-based detector with respect to convergence rate. On the other hand, the training-based detector performs better in the steady state, giving a lower excess mean-square error (MSE) for a given adaptation step size. A novel decision-directed LMS detector which achieves the low excess MSE of the training-based detector and the superior convergence performance of the blind detector is proposed.