Double-autoionization decay of resonantly excited single-electron states

Perturbation theory in the lowest non-vanishing order in interelectron interaction has been applied to the theoretical investigation of double-ionization decays of resonantly excited single-electron states. The formulae for the transition probabilities were derived in the LS coupling scheme, and the orbital angular momentum and spin selection rules were obtained. In addition to the formulae, which are exact in this order, three approximate expressions, which correspond to illustrative model mechanisms of the transition, were derived as limiting cases of the exact ones. Numerical results were obtained for the decay of the resonantly excited Kr 1 3d^{-1}5p[^1P] state which demonstrated quite clearly the important role of the interelectron interaction in double-ionization processes. On the other hand, the results obtained show that low-energy electrons can appear in the photoelectron spectrum below the ionization threshold of the 3d shell. As a function of the photon frequency, the yield of these low-energy electrons is strongly amplified by the resonant transition of the 3d electron to 5p (or to other discrete levels), acting as an intermediate state, when the photon frequency approaches that of the transition.

Influence of the electronic shell structure on the elastic scattering of heavy ions

The interatomic potential of the system I - I at intermediate and small distances is calculated from atomic DFS electron densities within a statistical model. Structures in the potential, due to the electronic shells, are investigated. Calculations of the elastic differential scattering cross section for small angles and several keV impact energies show a detailed peak pattern which can be correlated to individual electronic shell interaction.

A Computational Model for Observation in Quantum Mechanics

A computational model of observation in quantum mechanics is presented. The model provides a clean and simple computational paradigm which can be used to illustrate and possibly explain some of the unintuitive and unexpected behavior of some quantum mechanical systems. As examples, the model is used to simulate three seminal quantum mechanical experiments. The results obtained agree with the predictions of quantum mechanics (and physical measurements), yet the model is perfectly deterministic and maintains a notion of locality.

A Distributed Model for Mobile Robot Environment-Learning and Navigation

A distributed method for mobile robot navigation, spatial learning, and path planning is presented. It is implemented on a sonar-based physical robot, Toto, consisting of three competence layers: 1) Low-level navigation: a collection of reflex-like rules resulting in emergent boundary-tracing. 2) Landmark detection: dynamically extracts landmarks from the robot's motion. 3) Map learning: constructs a distributed map of landmarks. The parallel implementation allows for localization in constant time. Spreading of activation computes both topological and physical shortest paths in linear time. The main issues addressed are: distributed, procedural, and qualitative representation and computation, emergent behaviors, dynamic landmarks, minimized communication.

Uncertainty Propagation in Model-Based Recognition

Building robust recognition systems requires a careful understanding of the effects of error in sensed features. Error in these image features results in a region of uncertainty in the possible image location of each additional model feature. We present an accurate, analytic approximation for this uncertainty region when model poses are based on matching three image and model points, for both Gaussian and bounded error in the detection of image points, and for both scaled-orthographic and perspective projection models. This result applies to objects that are fully three- dimensional, where past results considered only two-dimensional objects. Further, we introduce a linear programming algorithm to compute the uncertainty region when poses are based on any number of initial matches. Finally, we use these results to extend, from two-dimensional to three- dimensional objects, robust implementations of alignmentt interpretation- tree search, and ransformation clustering.

Molecular computations for reactions and phase transitions: applications to protein stabilization, hydrates and catalysis

In this work we have made significant contributions in three different areas of interest: therapeutic protein stabilization, thermodynamics of natural gas clathrate-hydrates, and zeolite catalysis. In all three fields, using our various computational techniques, we have been able to elucidate phenomena that are difficult or impossible to explain experimentally. More specifically, in mixed solvent systems for proteins we developed a statistical-mechanical method to model the thermodynamic effects of additives in molecular-level detail. It was the first method demonstrated to have truly predictive (no adjustable parameters) capability for real protein systems. We also describe a novel mechanism that slows protein association reactions, called the “gap effect.” We developed a comprehensive picture of methioine oxidation by hydrogen peroxide that allows for accurate prediction of protein oxidation and provides a rationale for developing strategies to control oxidation. The method of solvent accessible area (SAA) was shown not to correlate well with oxidation rates. A new property, averaged two-shell water coordination number (2SWCN) was identified and shown to correlate well with oxidation rates. Reference parameters for the van der Waals Platteeuw model of clathrate-hydrates were found for structure I and structure II. These reference parameters are independent of the potential form (unlike the commonly used parameters) and have been validated by calculating phase behavior and structural transitions for mixed hydrate systems. These calculations are validated with experimental data for both structures and for systems that undergo transitions from one structure to another. This is the first method of calculating hydrate thermodynamics to demonstrate predictive capability for phase equilibria, structural changes, and occupancy in pure and mixed hydrate systems. We have computed a new mechanism for the methanol coupling reaction to form ethanol and water in the zeolite chabazite. The mechanism at 400°C proceeds via stable intermediates of water, methane, and protonated formaldehyde.

Model Order Reduction for Determining Bubble Parameters to Attain a Desired Fluid Surface Shape

In this paper, a new methodology for predicting fluid free surface shape using Model Order Reduction (MOR) is presented. Proper Orthogonal Decomposition combined with a linear interpolation procedure for its coefficient is applied to a problem involving bubble dynamics near to a free surface. A model is developed to accurately and efficiently capture the variation of the free surface shape with different bubble parameters. In addition, a systematic approach is developed within the MOR framework to find the best initial locations and pressures for a set of bubbles beneath the quiescent free surface such that the resultant free surface attained is close to a desired shape. Predictions of the free surface in two-dimensions and three-dimensions are presented.

A Log-linear model of grain size influence on the geochemistry of sediments

Sediment composition is mainly controlled by the nature of the source rock(s), and chemical (weathering) and physical processes (mechanical crushing, abrasion, hydrodynamic sorting) during alteration and transport. Although the factors controlling these processes are conceptually well understood, detailed quantification of compositional changes induced by a single process are rare, as are examples where the effects of several processes can be distinguished. The present study was designed to characterize the role of mechanical crushing and sorting in the absence of chemical weathering. Twenty sediment samples were taken from Alpine glaciers that erode almost pure granitoid lithologies. For each sample, 11 grain-size fractions from granules to clay (ø grades <-1 to >9) were separated, and each fraction was analysed for its chemical composition. The presence of clear steps in the box-plots of all parts (in adequate ilr and clr scales) against ø is assumed to be explained by typical crystal size ranges for the relevant mineral phases. These scatter plots and the biplot suggest a splitting of the full grain size range into three groups: coarser than ø=4 (comparatively rich in SiO2, Na2O, K2O, Al2O3, and dominated by “felsic” minerals like quartz and feldspar), finer than ø=8 (comparatively rich in TiO2, MnO, MgO, Fe2O3, mostly related to “mafic” sheet silicates like biotite and chlorite), and intermediate grains sizes (4≤ø <8; comparatively rich in P2O5 and CaO, related to apatite, some feldspar). To further test the absence of chemical weathering, the observed compositions were regressed against three explanatory variables: a trend on grain size in ø scale, a step function for ø≥4, and another for ø≥8. The original hypothesis was that the trend could be identified with weathering effects, whereas each step function would highlight those minerals with biggest characteristic size at its lower end. Results suggest that this assumption is reasonable for the step function, but that besides weathering some other factors (different mechanical behavior of minerals) have also an important contribution to the trend. Key words: sediment, geochemistry, grain size, regression, step function

Model-based objects recognition in man-made environments

We describe a model-based objects recognition system which is part of an image interpretation system intended to assist autonomous vehicles navigation. The system is intended to operate in man-made environments. Behavior-based navigation of autonomous vehicles involves the recognition of navigable areas and the potential obstacles. The recognition system integrates color, shape and texture information together with the location of the vanishing point. The recognition process starts from some prior scene knowledge, that is, a generic model of the expected scene and the potential objects. The recognition system constitutes an approach where different low-level vision techniques extract a multitude of image descriptors which are then analyzed using a rule-based reasoning system to interpret the image content. This system has been implemented using CEES, the C++ embedded expert system shell developed in the Systems Engineering and Automatic Control Laboratory (University of Girona) as a specific rule-based problem solving tool. It has been especially conceived for supporting cooperative expert systems, and uses the object oriented programming paradigm

A prediction model for establishing the disability degree in adults with spinal cord injury: results based on WHO-DAS II perspective

Objective: To establish a prediction model of the degree of disability in adults with Spinal CordInjury (SCI ) based on the use of the WHO-DAS II . Methods: The disability degree was correlatedwith three variable groups: clinical, sociodemographic and those related with rehabilitation services.A model of multiple linear regression was built to predict disability. 45 people with sci exhibitingdiverse etiology, neurological level and completeness participated. Patients were older than 18 andthey had more than a six-month post-injury. The WHO-DAS II and the ASIA impairment scale(AIS ) were used. Results: Variables that evidenced a significant relationship with disability were thefollowing: occupational situation, type of affiliation to the public health care system, injury evolutiontime, neurological level, partial preservation zone, ais motor and sensory scores and number ofclinical complications during the last year. Complications significantly associated to disability werejoint pain, urinary infections, intestinal problems and autonomic disreflexia. None of the variablesrelated to rehabilitation services showed significant association with disability. The disability degreeexhibited significant differences in favor of the groups that received the following services: assistivedevices supply and vocational, job or educational counseling. Conclusions: The best predictiondisability model in adults with sci with more than six months post-injury was built with variablesof injury evolution time, AIS sensory score and injury-related unemployment.

Estimation of electronic coupling in π -stacked donor-bridge-acceptor systems: correction of the two-state model

Comparison of donor-acceptor electronic couplings calculated within two-state and three-state models suggests that the two-state treatment can provide unreliable estimates of Vda because of neglecting the multistate effects. We show that in most cases accurate values of the electronic coupling in a π stack, where donor and acceptor are separated by a bridging unit, can be obtained as Ṽ da = (E2 - E1) μ12 Rda + (2 E3 - E1 - E2) 2 μ13 μ23 Rda2, where E1, E2, and E3 are adiabatic energies of the ground, charge-transfer, and bridge states, respectively, μij is the transition dipole moments between the states i and j, and Rda is the distance between the planes of donor and acceptor. In this expression based on the generalized Mulliken-Hush approach, the first term corresponds to the coupling derived within a two-state model, whereas the second term is the superexchange correction accounting for the bridge effect. The formula is extended to bridges consisting of several subunits. The influence of the donor-acceptor energy mismatch on the excess charge distribution, adiabatic dipole and transition moments, and electronic couplings is examined. A diagnostic is developed to determine whether the two-state approach can be applied. Based on numerical results, we showed that the superexchange correction considerably improves estimates of the donor-acceptor coupling derived within a two-state approach. In most cases when the two-state scheme fails, the formula gives reliable results which are in good agreement (within 5%) with the data of the three-state generalized Mulliken-Hush model

Numerical model of solid phase transformations governed by nucleation and growth: microstructure development during isothermal crystallization

A simple numerical model which calculates the kinetics of crystallization involving randomly distributed nucleation and isotropic growth is presented. The model can be applied to different thermal histories and no restrictions are imposed on the time and the temperature dependences of the nucleation and growth rates. We also develop an algorithm which evaluates the corresponding emerging grain-size distribution. The algorithm is easy to implement and particularly flexible, making it possible to simulate several experimental conditions. Its simplicity and minimal computer requirements allow high accuracy for two- and three-dimensional growth simulations. The algorithm is applied to explore the grain morphology development during isothermal treatments for several nucleation regimes. In particular, thermal nucleation, preexisting nuclei, and the combination of both nucleation mechanisms are analyzed. For the first two cases, the universal grain-size distribution is obtained. The high accuracy of the model is stated from its comparison to analytical predictions. Finally, the validity of the Kolmogorov-Johnson-Mehl-Avrami model SSSR, is verified for all the cases studied

Comparing meta-analysis and ecological-longitudinal analysis in time-series studies: a case study of the effects of air pollution on mortality in three Spanish cities

The objective of this paper is to introduce a diVerent approach, called the ecological-longitudinal, to carrying out pooled analysis in time series ecological studies. Because it gives a larger number of data points and, hence, increases the statistical power of the analysis, this approach, unlike conventional ones, allows the complementation of aspects such as accommodation of random effect models, of lags, of interaction between pollutants and between pollutants and meteorological variables, that are hardly implemented in conventional approaches. Design—The approach is illustrated by providing quantitative estimates of the short-termeVects of air pollution on mortality in three Spanish cities, Barcelona,Valencia and Vigo, for the period 1992–1994. Because the dependent variable was a count, a Poisson generalised linear model was first specified. Several modelling issues are worth mentioning. Firstly, because the relations between mortality and explanatory variables were nonlinear, cubic splines were used for covariate control, leading to a generalised additive model, GAM. Secondly, the effects of the predictors on the response were allowed to occur with some lag. Thirdly, the residual autocorrelation, because of imperfect control, was controlled for by means of an autoregressive Poisson GAM. Finally, the longitudinal design demanded the consideration of the existence of individual heterogeneity, requiring the consideration of mixed models. Main results—The estimates of the relative risks obtained from the individual analyses varied across cities, particularly those associated with sulphur dioxide. The highest relative risks corresponded to black smoke in Valencia. These estimates were higher than those obtained from the ecological-longitudinal analysis. Relative risks estimated from this latter analysis were practically identical across cities, 1.00638 (95% confidence intervals 1.0002, 1.0011) for a black smoke increase of 10 μg/m3 and 1.00415 (95% CI 1.0001, 1.0007) for a increase of 10 μg/m3 of sulphur dioxide. Because the statistical power is higher than in the individual analysis more interactions were statistically significant,especially those among air pollutants and meteorological variables. Conclusions—Air pollutant levels were related to mortality in the three cities of the study, Barcelona, Valencia and Vigo. These results were consistent with similar studies in other cities, with other multicentric studies and coherent with both, previous individual, for each city, and multicentric studies for all three cities

Integrated management of urban wastewater systems: a model-based approach

The main objective pursued in this thesis targets the development and systematization of a methodology that allows addressing management problems in the dynamic operation of Urban Wastewater Systems. The proposed methodology will suggest operational strategies that can improve the overall performance of the system under certain problematic situations through a model-based approach. The proposed methodology has three main steps: The first step includes the characterization and modeling of the case-study, the definition of scenarios, the evaluation criteria and the operational settings that can be manipulated to improve the system’s performance. In the second step, Monte Carlo simulations are launched to evaluate how the system performs for a wide range of operational settings combinations, and a global sensitivity analysis is conducted to rank the most influential operational settings. Finally, the third step consists on a screening methodology applying a multi-criteria analysis to select the best combinations of operational settings.

Cap a un model per interpretar i facilitar l'aprendre: estratègies i recursos per a la reflexió-acció en i des de la pràctica

1.- L'enquadrament d'aquest treball de recerca s'ha fet en i des de la praxis. EI que interessa és descobrir i proposar instruments pedagògics d'ajuda, assequibles i contextualitzats, especialment en el terreny de la comunicació i la interacció Educador-Educand. La metodologia que s'ha fet servir és de caire qualitatiu, etnogràfic, en un enfocament basat en la investigació-acció. La visió de la persona és volgudament holística; els sentiments, els significats, I' orientació personal, I' autodirecció. esdevenen elements centrals. La hipòtesi de treball, en la qual es fonamenta la recerca, podria formular-se així: 'En la pràctica, els Educadors, d'una forma més o menys reflexiva, perceben i interpreten el procés d'aprendre dels Educands; hi intervenen, el mediatitzen; n'avaluen la direcció i l'encert". A partir d'aquest supòsit, l'investigador veu convenient donar resposta a tres qüestions centrals: A) Com comprenem i interpretem els Educadors el procés d'aprendre dels Educands?; B) Quin tipus d'intervenció resultarà adient per promoure i/o facilitar l'aprendre?; C) Amb quins instruments i estratègies comptem per ajudar pedagògicament? 2.- Per llegir l'aprendre, l'investigador fa ús d'un model mental, indispensable per ordenar les dades de l'experiència. Convé, per tant, explicitar-lo, fer-ne ciència, coneixement compartit. En aquesta direcció de treball se li plantegen dos tipus d'interrogants: A) Quins són els elements comuns a qualsevol experiència d'aprenentatge?; Quina mena d'activitat o experiència personal desenvolupen tots els Educands; i B) Com es manifesta aquesta experiència? Amb quins indicadors? Quina mena de "text" llegeix l'Educador per orientar la seva intervenció d'ajuda? 3.- L'aprenentatge. en aquest treball, és considerat per l'investigador com la resultant de tres processos personals: el posicionament, l'estratègia i l'avaluació. Quan l'Educador vol compartir amb l'Educand el seu procés idiosincràtic d'aprendre, procura reconstruir amb ell aquestes tres accions bàsiques: A) Com es posiciona: què tem o desitja, què creu, què espera, quines expectatives viu, com es motiva? B) Quines són les seves pautes d'actuació: com treballa, com memoritza, com recupera la informació que té a la memòria, què fa davant d'un problema... ? C) Què busca; què és important per a ella; què pretén... ? 4.- Davant la complexitat dels missatges emesos per l'Educand l'investigador opta per llegir tres tipus de "textos": els productes i els resultats; les conductes; i els missatges parlats. Entre tots tres, pensa, podrà trobar elements i indicadors adequats per fonamentar, sempre hipotèticament, la seva actuació pedagògica. 5.- Procura sobretot detectar i fer existir els èxits, aquells productes i/o resultats que l'Educand troba valuosos, per tal d'ajudar-lo a prendre consciència dels seu repertori personal d'estratègies i capacitats. En aquest àmbit es proposen tres actituds o enfocaments del treball d'ajuda: A) El primer fa referència a la presa de consciència de l'estratègia personal, que s'amaga darrera el producte valorat. B) El segon apunta cap al respecte per l'estratègia que cadascú executa i, per tant, li és familiar. L'Educand la necessita. Es la seva. Es troba en la seva experiència, encara que no necessàriament existeixi en la seva construcció conscient. C) El tercer ,el duu a valorar l'estratègia d'acord amb les finalitats de l'Educand. La seva adequació es legitima pel que es proposa. Partim del supòsit que tota conducta es troba dirigida per un propòsit a vegades difícil de copsar i no sempre recomanable per a l'Educand. 6.- La conducta percebuda de l'Educand és entesa com un missatge, un conjunt d'indicadors de la seva activitat contextualitzada, interna i externa; missatge que, en relació amb altres, com els productes i les verbalitzacions, manifesta fragments dels seus significats, projectes, estratègies, valors. Es fa un èmfasi especial en les conductes "internes", els gestos mentals, l'acció interior, tramesa per mitja de microcomportaments sovint no conscient, i certificada per mitjà de la verbalització del viscut. 7.- Parlar amb l'Educand suposa dues menes d'accions: escoltar i emetre. Escoltem per comprendre; emetem per perfilar la comprensió i també per ajudar. En l'emissió, el missatge pedagògic té dues funcions: a) rellançar i orientar el pensament i l'autoexploració de l'Educand; i b) influir per tal que desenvolupi amb èxit el seu projecte d'aprendre. Interessa d'una manera especial ajudar a integrar en la consciència de l'Educand aquests elements de la seva experiència que poden facilitar-li l'adquisició del coneixement. I entenem que, en aquesta empresa, la paraula i la interacció verbal poden tenir-hi un joc important. Per aquesta raó s'ha considerat necessari oferir un model d'anàlisi de la interacció i els missatges verbals. 8.- "Les persones aprenen sempre, amb recursos, processos i sistemes de valoració idiosincràtics, per fa qual cosa la seva orientació en el context esdevé un referent central en el disseny de l'ajuda pedagògica i en la seva avaluació". Aquesta és la hipòtesi de sortida per dissenyar la intervenció pedagògica. Tothom aprèn, inevitablement; la qüestió és quina cosa està aprenent i de quina manera els seus resultats d'ara són mediatitzats per l'experiència passada i, alhora, condicionen el seu aprendre futur. L'aprenent es posiciona, anticipa el procés d' aprendre, valora la seva. capacitat per desenvolupar-lo amb èxit, es motiva en una determinada direcció, d'acord amb la seva experiència, els seus aprenentatges anteriors. Executa estratègies, mostra un tipus d'intel·ligència, una forma personal de processar la informació. Pretén quelcom. És un sistema obert en relació amb el medi: hi ha uns valors que dirigeixen la seva presa de decisions. Utilitza uns criteris propis, una gamma personal d'opcions conscients. Avalua el que fa, el resultat que obté i la seva capacitat personal. 9.- L'ajuda pedagògica que I' autor proposa s'encamina sobretot a facilitar en l'Educand la descoberta dels seus propis recursos. Es tracta de portar-lo cap a la consideració atenta de la seva pròpia experiència, per amplificar-la i fer-la existir com a recurs conscient . Ha dibuixat i experimentat tres conjunts d'intervenció cadascun enfocat vers un àmbit de l'experiència d'aprendre, el qual col·loca com a prioritari, sense oblidar qualsevol dels altres que pugui ser rellevant, per comprendre o ajudar. A) Intervenció sobre el posicionament. En aquest àmbit enfoca l'estil de motivació que executa l'Educand, mira de corregir-lo, si cal, a partir de l'anàlisi i la comprensió de les seves formes de motivar-se quan ell viu l'èxit. Treballa proposant objectius paradoxals de fracàs gairebé impossible, buscant l'assoliment de petits èxits, potser aparentment insignificants, però estratègics; prescriu l'automatisme, per modificar-lo si l'Educand ho desitja; comprova el procés d'anticipació de I' experiència que l'aprenent es construeix per orientar-se; l'ajuda a contextualitzar anticipació i a fer ús dels seus Ilenguatges interns més eficaços i còmodes;... B) Intervenció sobre les estratègies i processos. En un segon enfocament, no necessàriament posterior al descrit, considera les estratègies de I'Educand, també a partir dels seus encerts i èxits. Mira de portar-lo cap a fa descripció i presa de consciència de les seves maneres de fer mes còmodes i segures, les que lliguen amb les seves preferències cerebrals. Quan viu dificultats, el convida a explorar les excepcions, els moments en els quals les seves realitzacions són satisfactòries. Pretén sobretot modificar les seves creences limitants, posant-lo en conflicte amb els fets de l'experiència. A vegades, caldrà facilitar l'adquisició d'estratègies i procediments nous que l'Educand considera plausibles. Es tracta específicament de fer existir opcions noves d'actuació per tal d'assolir allò que vol i/o necessita. C) Intervenció sobre el sistema de valors de l'Educand. L'Educand viu uns valors, els quals expliquen el seu món intern les conductes que realitza i els resultats que obté. Aquest àmbit és col·locat, en el model, al centre del procés d'aprendre. Hom actua amb propòsits determinats, no necessariament conscients. L'obertura de la persona a l'experiència d'aprendre es dirigeix segons criteris i valors irrenunciables. 10.- L 'Educador procura compartir els objectius de l'Educand i els seus projectes per assolir-los; vol tanmateix que se'n faci coneixedor i director responsable. Per a això li convé preguntar-se per quina mena d'experiència està desenvolupant i quin sentit ecològic te per a ell. L'Educador, el seu model del món, la seva persona, està compromès en el procés d'ajuda. No és només un tècnic que aplica recursos objectius. El seu model de comunicació, el seu pensament, les seves expectatives i anticipacions, tenen un pes considerable en el tipus d'intervenció pedagògica que durà a terme i, d'escreix, en el tipus d' aprenentatge que facilita. En la intervenció, l'Educador parteix d'una avaluació intencionadament positiva, centrada en els recursos i les solucions, en la metacognició i l'autoregulació dels processos, a partir de premisses que pressuposen l'èxit personal.