Structure of spectra of linear operators in Banach spaces

Descriptive characterizations of the point, the continuous, and the residual spectra of operators in Banach spaces are put forward. In particular, necessary and sufficient conditions for three disjoint subsets of the complex plane to be the point spectrum, the continuous spectrum, and the residual spectrum of a linear continuous operator in a separable Banach space are obtained.

Model selection approaches for non-linear system identification: a review

The identification of non-linear systems using only observed finite datasets has become a mature research area over the last two decades. A class of linear-in-the-parameter models with universal approximation capabilities have been intensively studied and widely used due to the availability of many linear-learning algorithms and their inherent convergence conditions. This article presents a systematic overview of basic research on model selection approaches for linear-in-the-parameter models. One of the fundamental problems in non-linear system identification is to find the minimal model with the best model generalisation performance from observational data only. The important concepts in achieving good model generalisation used in various non-linear system-identification algorithms are first reviewed, including Bayesian parameter regularisation and models selective criteria based on the cross validation and experimental design. A significant advance in machine learning has been the development of the support vector machine as a means for identifying kernel models based on the structural risk minimisation principle. The developments on the convex optimisation-based model construction algorithms including the support vector regression algorithms are outlined. Input selection algorithms and on-line system identification algorithms are also included in this review. Finally, some industrial applications of non-linear models are discussed.

Fault reconstruction in linear dynamic systems using multivariate statistics

Treasure et al. (2004) recently proposed a new sub space-monitoring technique, based on the N4SID algorithm, within the multivariate statistical process control framework. This dynamic-monitoring method requires considerably fewer variables to be analysed when compared with dynamic principal component analysis (PCA). The contribution charts and variable reconstruction, traditionally employed for static PCA, are analysed in a dynamic context. The contribution charts and variable reconstruction may be affected by the ratio of the number of retained components to the total number of analysed variables. Particular problems arise if this ratio is large and a new reconstruction chart is introduced to overcome these. The utility of such a dynamic contribution chart and variable reconstruction is shown in a simulation and by application to industrial data from a distillation unit.

Insight into the solvent effect: A density functional theory study of cisplatin hydrolysis

The solvent effect on reactions in solutions is crucial for many systems. In this study, the reaction barrier with respect to the number of solvent molecules included in the system is systematically studied using density function theory calculations. Our results show that the barriers rapidly converge with respect to the number of solvent molecules. The solvent effect is investigated by calculating cisplatin hydrolysis in several types of solvents. The results are analyzed and a linear relationship between the reaction barrier and the interaction strength of solvent-reactants is found. Insight into the general solvent effect is obtained. (c) 2006 American Institute of Physics.

C-H bond activation over metal oxides: A new insight into the dissociation kinetics from density functional theory

The C-H activation on metal oxides is a fundamental process in chemistry. In this paper, we report a density functional theory study on the process of the C-H activation of CH4 on Pd(111), Pt(111), Ru(0001), Tc(0001), Cu(111), PdO(001), PdO(110), and PdO(100). A linear relationship between the C-H activation barrier and the chemisorption in the dissociation final state on the metal surfaces is obtained, which is consistent with the work in the literature. However, the relationship is poor on the metal oxide surfaces. Instead, a strong linear correlation between the barrier and the lattice O-H bond strength is found on the oxides. The new linear relationship is analyzed and the physical origin is identified. (c) 2008 American Institute of Physics.

Insight into association reactions on metal surfaces: Density-functional theory studies of hydrogenation reactions on Rh(111)

Hydrogenation reaction, as one of the simplest association reactions on surfaces, is of great importance both scientifically and technologically. They are essential steps in many industrial processes in heterogeneous catalysis, such as ammonia synthesis (N-2+3H(2)-->2NH(3)). Many issues in hydrogenation reactions remain largely elusive. In this work, the NHx (x=0,1,2) hydrogenation reactions (N+H-->NH, NH+H-->NH2 and NH2+H-->NH3) on Rh(111) are used as a model system to study the hydrogenation reactions on metal surfaces in general using density-functional theory. In addition, C and O hydrogenation (C+H-->CH and O+H-->OH) and several oxygenation reactions, i.e., C+O, N+O, O+O reactions, are also calculated in order to provide a further understanding of the barrier of association reactions. The reaction pathways and the barriers of all these reactions are determined and reported. For the C, N, NH, and O hydrogenation reactions, it is found that there is a linear relationship between the barrier and the valency of R (R=C, N, NH, and O). Detailed analyses are carried out to rationalize the barriers of the reactions, which shows that: (i) The interaction energy between two reactants in the transition state plays an important role in determining the trend in the barriers; (ii) there are two major components in the interaction energy: The bonding competition and the direct Pauli repulsion; and (iii) the Pauli repulsion effect is responsible for the linear valency-barrier trend in the C, N, NH, and O hydrogenation reactions. For the NH2+H reaction, which is different from other hydrogenation reactions studied, the energy cost of the NH2 activation from the IS to the TS is the main part of the barrier. The potential energy surface of the NH2 on metal surfaces is thus crucial to the barrier of NH2+H reaction. Three important factors that can affect the barrier of association reactions are generalized: (i) The bonding competition effect; (ii) the local charge densities of the reactants along the reaction direction; and (iii) the potential energy surface of the reactants on the surface. The lowest energy pathway for a surface association reaction should correspond to the one with the best compromise of these three factors. (C) 2003 American Institute of Physics.

Disturbance attenuation in linear systems via dynamical compensators: A parametric eigenstructure assignment approach

A simple approach is proposed for disturbance attenuation in multivariable linear systems via dynamical output compensators based on complete parametric eigenstructure assignment. The basic idea is to minimise the H-2 norm of the disturbance-output transfer function using the design freedom provided by eigenstructure assignment. For robustness, the closed-loop system is restricted to be nondefective. Besides the design parameters, the closed-loop eigenvalues are also optimised within desired regions on the left-half complex plane to ensure both closed-loop stability and dynamical performance. With the proposed approach, additional closed-loop specifications can be easily achieved. As a demonstration, robust pole assignment, in the sense that the closed-loop eigenvalues are as insensitive as possible to open-loop system parameter perturbations, is treated. Application of the proposed approach to robust control of a magnetic bearing with a pair of opposing electromagnets and a rigid rotor is discussed.

Linear and nonlinear properties of Rao-dust-Alfven waves in magnetized plasmas

The linear and nonlinear properties of the Rao-dust-magnetohydrodynamic (R-D-MHD) waves in a dusty magnetoplasma are studied. By employing the inertialess electron equation of motion, inertial ion equation of motion, Ampere's law, Faraday's law, and the continuity equation in a plasma with immobile charged dust grains, the linear and nonlinear propagation of two-dimensional R-D-MHD waves are investigated. In the linear regime, the existence of immobile dust grains produces the Rao cutoff frequency, which is proportional to the dust charge density and the ion gyrofrequency. On the other hand, the dynamics of amplitude modulated R-D-MHD waves is governed by the cubic nonlinear Schrodinger equation. The latter has been derived by using the reductive perturbation technique and the two-timescale analysis which accounts for the harmonic generation nonlinearity in plasmas. The stability of the modulated wave envelope against non-resonant perturbations is studied. Finally, the possibility of localized envelope excitations is discussed. (C) 2004 American Institute of Physics.

Exact theory for localized envelope modulated electrostatic wavepackets in space and dusty plasmas

Abundant evidence for the occurrence of modulated envelope plasma wave packets is provided by recent satellite missions. These excitations are characterized by a slowly varying localized envelope structure, embedding the fast carrier wave, which appears to be the result of strong modulation of the wave amplitude. This modulation may be due to parametric interactions between different modes or, simply, to the nonlinear (self-)interaction of the carrier wave. A generic exact theory is presented in this study, for the nonlinear self-modulation of known electrostatic plasma modes, by employing a collisionless fluid model. Both cold (zero-temperature) and warm fluid descriptions are discussed and the results are compared. The (moderately) nonlinear oscillation regime is investigated by applying a multiple scale technique. The calculation leads to a Nonlinear Schrodinger-type Equation (NLSE), which describes the evolution of the slowly varying wave amplitude in time and space. The NLSE admits localized envelope (solitary wave) solutions of bright(pulses) or dark- (holes, voids) type, whose characteristics (maximum amplitude, width) depend on intrinsic plasma parameters. Effects like amplitude perturbation obliqueness (with respect to the propagation direction), finite temperature and defect (dust) concentration are explicitly considered. Relevance with similar highly localized modulated wave structures observed during recent satellite missions is discussed.

Ground state of low-dimensional dipolar gases: Linear and zigzag chains

We study the ground-state phase diagram of ultracold dipolar gases in highly anisotropic traps. Starting from a one-dimensional geometry, by ramping down the transverse confinement along one direction, the gas reaches various planar distributions of dipoles. At large linear densities, when the dipolar gas exhibits a crystal-like phase, critical values of the transverse frequency exist below which the configuration exhibits transverse patterns. These critical values are found by means of a classical theory, and are in full agreement with classical Monte Carlo simulations. The study of the quantum system is performed numerically with Monte Carlo techniques and shows that the quantum fluctuations smoothen the transition and make it completely disappear in a gas phase. These predictions could be experimentally tested and would allow one to reveal the effect of zero-point motion on self-organized mesoscopic structures of matter waves, such as the transverse pattern of the zigzag chain.

Testing metabolic scaling theory using intraspecific allometries in Antarctic microarthropods

Quantitative scaling relationships among body mass, temperature and metabolic rate of organisms are still controversial, while resolution may be further complicated through the use of different and possibly inappropriate approaches to statistical analysis. We propose the application of a modelling strategy based on the theoretical approach of Akaike's information criteria and non-linear model fitting (nlm). Accordingly, we collated and modelled available data at intraspecific level on the individual standard metabolic rate of Antarctic microarthropods as a function of body mass (M), temperature (T), species identity (S) and high rank taxa to which species belong (G) and tested predictions from metabolic scaling theory (mass-metabolism allometric exponent b = 0.75, activation energy range 0.2-1.2 eV). We also performed allometric analysis based on logarithmic transformations (lm). Conclusions from lm and nlm approaches were different. Best-supported models from lm incorporated T, M and S. The estimates of the allometric scaling exponent linking body mass and metabolic rate resulted in a value of 0.696 +/- 0.105 (mean +/- 95% CI). In contrast, the four best-supported nlm models suggested that both the scaling exponent and activation energy significantly vary across the high rank taxa (Collembola, Cryptostigmata, Mesostigmata and Prostigmata) to which species belong, with mean values of b ranging from about 0.6 to 0.8. We therefore reached two conclusions: 1, published analyses of arthropod metabolism based on logarithmic data may be biased by data transformation; 2, non-linear models applied to Antarctic microarthropod metabolic rate suggest that intraspecific scaling of standard metabolic rate in Antarctic microarthropods is highly variable and can be characterised by scaling exponents that greatly vary within taxa, which may have biased previous interspecific comparisons that neglected intraspecific variability.

Alfvén Waves in the Solar Atmosphere: From Theory to Observations

Alfvén waves are considered to be viable transporters of the non-thermal energy required to heat the Sun's quiescent atmosphere. An abundance of recent observations, from state-of-the-art facilities, have reported the existence of Alfvén waves in a range of chromospheric and coronal structures. Here, we review the progress made in disentangling the characteristics of transverse kink and torsional linear magnetohydrodynamic (MHD) waves. We outline the simple, yet powerful theory describing their basic properties in (non-)uniform magnetic structures, which closely resemble the building blocks of the real solar atmosphere.

Pressure anisotropy effects on nonlinear electrostatic excitations in magnetized electron-positron-ion plasmas

The propagation of linear and nonlinear electrostatic waves is investigated in a magnetized anisotropic electron-positron-ion (e-p-i) plasma with superthermal electrons and positrons. A two-dimensional plasma geometry is assumed. The ions are assumed to be warm and anisotropic due to an external magnetic field. The anisotropic ion pressure is defined using the double adiabatic Chew-Golberger-Low (CGL) theory. In the linear regime, two normal modes are predicted, whose characteristics are investigated parametrically, focusing on the effect of superthermality of electrons and positrons, ion pressure anisotropy, positron concentration and magnetic field strength. A Zakharov-Kuznetsov (ZK) type equation is derived for the electrostatic potential (disturbance) via a reductive perturbation method. The parametric role of superthermality, positron content, ion pressure anisotropy and magnetic field strength on the characteristics of solitary wave structures is investigated. Following Allen and Rowlands [J. Plasma Phys. 53, 63 (1995)], we have shown that the pulse soliton solution of the ZK equation is unstable to oblique perturbations, and have analytically traced the dependence of the instability growth rate on superthermality and ion pressure anisotropy.

An Energy Descriptor To Quantify Methane Selectivity in Fischer-Tropsch Synthesis:A Density Functional Theory Study

Selectivity is a fundamental issue in heterogeneous catalysis. In this study, the CH(4) selectivity in Fischer-Tropsch synthesis is chosen to be investigated: CH4 selectivity on Rh, Co, Ru, Fe, and Re surfaces is computed by first-principles methods. In conjunction with kinetic analyses, we are able to derive the effective barrier difference between methane formation and chain growth (Delta E(eff)) to quantify the CH(4) selectivity. By using this energy descriptor, the ranking of methane selectivity predicted from density functional theory (DFT) calculations is consistent with experimental work. Moreover, a linear correlation between Delta E(eff) and the chemisorption energy of C + 4H (Delta H) is found. This fundamental finding possesses the following significance: (i) it shows that the selectivity, which appears to have kinetic characteristics, is largely determined by thermodynamic properties; and (ii) it suggests that an increase of the binding strength of C + 4H will suppress methane selectivity.

GRADIENT CORRECTIONS IN DENSITY-FUNCTIONAL THEORY CALCULATIONS FOR SURFACES - CO ON PD(110)

Ab initio total energy calculations have been performed for CO chemisorption on Pd(110). Local density approximation (LDA) calculations yield chemisorption energies which are significantly higher than experimental values but inclusion of the generalised gradient approximation (GGA) gives better agreement. In general, sites with higher coordination of the adsorbate to surface atoms lead to a larger degree of overbinding with LDA, and give larger corrections with GGA. The reason is discussed using a first-order perturbation approximation. It is concluded that this may be a general failure of LDA for chemisorption energy calculations. This conclusion may be extended to many surface calculations, such as potential energy surfaces for diffusion.