Advanced density functional theory methods for materials science

In this work we chiefly deal with two broad classes of problems in computational materials science, determining the doping mechanism in a semiconductor and developing an extreme condition equation of state. While solving certain aspects of these questions is well-trodden ground, both require extending the reach of existing methods to fully answer them. Here we choose to build upon the framework of density functional theory (DFT) which provides an efficient means to investigate a system from a quantum mechanics description.

Zinc Phosphide (Zn₃P₂) could be the basis for cheap and highly efficient solar cells. Its use in this regard is limited by the difficulty in n-type doping the material. In an effort to understand the mechanism behind this, the energetics and electronic structure of intrinsic point defects in zinc phosphide are studied using generalized Kohn-Sham theory and utilizing the Heyd, Scuseria, and Ernzerhof (HSE) hybrid functional for exchange and correlation. Novel 'perturbation extrapolation' is utilized to extend the use of the computationally expensive HSE functional to this large-scale defect system. According to calculations, the formation energy of charged phosphorus interstitial defects are very low in n-type Zn₃P₂ and act as 'electron sinks', nullifying the desired doping and lowering the fermi-level back towards the p-type regime. Going forward, this insight provides clues to fabricating useful zinc phosphide based devices. In addition, the methodology developed for this work can be applied to further doping studies in other systems.

Accurate determination of high pressure and temperature equations of state is fundamental in a variety of fields. However, it is often very difficult to cover a wide range of temperatures and pressures in an laboratory setting. Here we develop methods to determine a multi-phase equation of state for Ta through computation. The typical means of investigating thermodynamic properties is via ’classical’ molecular dynamics where the atomic motion is calculated from Newtonian mechanics with the electronic effects abstracted away into an interatomic potential function. For our purposes, a ’first principles’ approach such as DFT is useful as a classical potential is typically valid for only a portion of the phase diagram (i.e. whatever part it has been fit to). Furthermore, for extremes of temperature and pressure quantum effects become critical to accurately capture an equation of state and are very hard to capture in even complex model potentials. This requires extending the inherently zero temperature DFT to predict the finite temperature response of the system. Statistical modelling and thermodynamic integration is used to extend our results over all phases, as well as phase-coexistence regions which are at the limits of typical DFT validity. We deliver the most comprehensive and accurate equation of state that has been done for Ta. This work also lends insights that can be applied to further equation of state work in many other materials.

Classical and Quantum Effects in Plasmonic Metals

The field of plasmonics exploits the unique optical properties of metallic nanostructures to concentrate and manipulate light at subwavelength length scales. Metallic nanostructures get their unique properties from their ability to support surface plasmons– coherent wave-like oscillations of the free electrons at the interface between a conductive and dielectric medium. Recent advancements in the ability to fabricate metallic nanostructures with subwavelength length scales have created new possibilities in technology and research in a broad range of applications.

In the first part of this thesis, we present two investigations of the relationship between the charge state and optical state of plasmonic metal nanoparticles. Using experimental bias-dependent extinction measurements, we derive a potential- dependent dielectric function for Au nanoparticles that accounts for changes in the physical properties due to an applied bias that contribute to the optical extinction. We also present theory and experiment for the reverse effect– the manipulation of the carrier density of Au nanoparticles via controlled optical excitation. This plasmoelectric effect takes advantage of the strong resonant properties of plasmonic materials and the relationship between charge state and optical properties to eluci- date a new avenue for conversion of optical power to electrical potential.

The second topic of this thesis is the non-radiative decay of plasmons to a hot-carrier distribution, and the distribution’s subsequent relaxation. We present first-principles calculations that capture all of the significant microscopic mechanisms underlying surface plasmon decay and predict the initial excited carrier distributions so generated. We also preform ab initio calculations of the electron-temperature dependent heat capacities and electron-phonon coupling coefficients of plasmonic metals. We extend these first-principle methods to calculate the electron-temperature dependent dielectric response of hot electrons in plasmonic metals, including direct interband and phonon-assisted intraband transitions. Finally, we combine these first-principles calculations of carrier dynamics and optical response to produce a complete theoretical description of ultrafast pump-probe measurements, free of any fitting parameters that are typical in previous analyses.

Methods of monitoring of metro lining in Prague

There are several reasons for monitoring of underground structures and they have already been discussed many times, e.g. from the view of ageing or state after accidental event like flooding of Prague metro in 2002. Monitoring of Prague metro is realized in the framework of international research project sponsored by ESF-S3T. The monitoring methods used in Prague are either classical one or new or developing one. The reason for different monitoring methods is the different precision of each method and also for cross-checking between them and their evaluation. Namely we use convergence, tiltmetres, crackmetres, geophysical methods, laser scanning, computer vision and finally installation of MEMS monitoring devices. In the paper more details of each method and obtained results will be presented. The monitoring methods are complemented by wireless data collection and transfer for real-time monitoring. © 2012 Taylor & Francis Group.

Indexing Methods for Efficient Multiclass Recognition

Many real world image analysis problems, such as face recognition and hand pose estimation, involve recognizing a large number of classes of objects or shapes. Large margin methods, such as AdaBoost and Support Vector Machines (SVMs), often provide competitive accuracy rates, but at the cost of evaluating a large number of binary classifiers, thus making it difficult to apply such methods when thousands or millions of classes need to be recognized. This thesis proposes a filter-and-refine framework, whereby, given a test pattern, a small number of candidate classes can be identified efficiently at the filter step, and computationally expensive large margin classifiers are used to evaluate these candidates at the refine step. Two different filtering methods are proposed, ClassMap and OVA-VS (One-vs.-All classification using Vector Search). ClassMap is an embedding-based method, works for both boosted classifiers and SVMs, and tends to map the patterns and their associated classes close to each other in a vector space. OVA-VS maps OVA classifiers and test patterns to vectors based on the weights and outputs of weak classifiers of the boosting scheme. At runtime, finding the strongest-responding OVA classifier becomes a classical vector search problem, where well-known methods can be used to gain efficiency. In our experiments, the proposed methods achieve significant speed-ups, in some cases up to two orders of magnitude, compared to exhaustive evaluation of all OVA classifiers. This was achieved in hand pose recognition and face recognition systems where the number of classes ranges from 535 to 48,600.

Finite size effects in the presence of a chemical potential: A study in the classical nonlinear O(2) sigma model

In the presence of a chemical potential, the physics of level crossings leads to singularities at zero temperature, even when the spatial volume is finite. These singularities are smoothed out at a finite temperature but leave behind nontrivial finite size effects which must be understood in order to extract thermodynamic quantities using Monte Carlo methods, particularly close to critical points. We illustrate some of these issues using the classical nonlinear O(2) sigma model with a coupling β and chemical potential μ on a 2+1-dimensional Euclidean lattice. In the conventional formulation this model suffers from a sign problem at nonzero chemical potential and hence cannot be studied with the Wolff cluster algorithm. However, when formulated in terms of the worldline of particles, the sign problem is absent, and the model can be studied efficiently with the "worm algorithm." Using this method we study the finite size effects that arise due to the chemical potential and develop an effective quantum mechanical approach to capture the effects. As a side result we obtain energy levels of up to four particles as a function of the box size and uncover a part of the phase diagram in the (β,μ) plane. © 2010 The American Physical Society.

New results on a classical operator

It is remarkable how the classical Volterra integral operator, which was one of the first operators which attracted mathematicians' attention, is still worth of being studied. In this essentially survey work, by collecting some of the very recent results related to the Volterra operator, we show that there are new (and not so new) concepts that are becoming known only at the present days. Discovering whether the Volterra operator satisfies or not a given operator property leads to new methods and ideas that are useful in the setting of Concrete Operator Theory as well as the one of General Operator Theory. In particular, a wide variety of techniques like summability kernels, theory of entire functions, Gaussian cylindrical measures, approximation theory, Laguerre and Legendre polynomials are needed to analyze different properties of the Volterra operator. We also include a characterization of the commutator of the Volterra operator acting on L-P[0, 1], 1

Gene-environment interactions and aging visual function: a classical twin study.

OBJECTIVE:
To elucidate the contribution of environmental versus genetic factors to the significant losses in visual function associated with normal aging.
DESIGN:
A classical twin study.
PARTICIPANTS:
Forty-two twin pairs (21 monozygotic and 21 dizygotic; age 57-75 years) with normal visual acuity recruited through the Australian Twin Registry.
METHODS:
Cone function was evaluated by establishing absolute cone contrast thresholds to flicker (4 and 14 Hz) and isoluminant red and blue colors under steady state adaptation. Adaptation dynamics were determined for both cones and rods. Bootstrap resampling was used to return robust intrapair correlations for each parameter.
MAIN OUTCOME MEASURES:
Psychophysical thresholds and adaptational time constants.
RESULTS:
The intrapair correlations for all color and flicker thresholds, as well as cone absolute threshold, were significantly higher in monozygotic compared with dizygotic twin pairs (P<0.05). Rod absolute thresholds (P = 0.28) and rod and cone recovery rate (P = 0.83; P = 0.79, respectively) did not show significant differences between monozygotic and dizygotic twins in their intrapair correlations, indicating that steady-state cone thresholds and flicker thresholds have a marked genetic contribution, in contrast with rod thresholds and adaptive processes, which are influenced more by environmental factors over a lifetime.
CONCLUSIONS:
Genes and the environment contribute differently to important neuronal processes in the retina and the role they may play in the decline in visual function as we age. Consequently, retinal structures involved in rod thresholds and adaptive processes may be responsive to appropriate environmental manipulation. Because the functions tested are commonly impaired in the early stages of age-related macular degeneration, which is known to have a multifactorial etiology, this study supports the view that pathogenic pathways early in the disease may be altered by appropriate environmental intervention.

Heritability of the spatial distribution and peak density of macular pigment:a classical twin study

Purpose: To elucidate the heritability of peak density and spatial width of macular pigment (MP) using a Classical Twin Study.

Methods: Fundus autofluorescence images were obtained at 488?nm from 86 subjects or 43 twin pairs (21 monozygotic (MZ) and 22 dizygotic (DZ)) (27 male, 59 female) aged from 55 to 76 years (mean 62.2±5.3 years). The relative topographic distribution of MP was measured using a grey scale of intensity (0-255 units) in a 7° eccentricity around the fovea. Relative peak MP density (rPMPD) and relative spatial distribution of MP (rSDMP) were used as the main outcome measure in the statistical analysis.

Results: A significantly higher correlation was found within MZ pairs as compared with that within DZ pairs for rPMPD, (r=0.99, 95% confidence interval (95% CI) 0.93 to 1.00) and 0.22, 95% CI -0.34 to 0.71), respectively, suggesting strong heritability of this trait. When rSDMP was compared, there was no significant difference between the correlations within MZ pairs (r=0.48, 95% CI -0.02 to 0.83) and DZ pairs (r=0.63, 95% CI 0.32 to 0.83), thus rSDMP is unlikely to have a considerable heritable component. In addition, there was no difference between any MP parameter when normal maculae were compared with early age-related macular degeneration (AMD) (rPMPD 0.36 vs 0.34, t=1.18 P=0.243, rSDMP 1.75 vs 1.75, t=0.028 P=0.977).ConclusionsrPMPD is a strongly heritable trait whereas rSDMP has minimal genetic influence and a greater influence by environmental factors. The presence of macular changes associated with early AMD did not appear to influence any of these pigment parameters. © 2012 Macmillan Publishers Limited All rights reserved 0950-222X/12

Optimal Scheduling Methods to Integrate Plug-In Electric Vehicles with the Power System: A Review

The introduction of the Tesla in 2008 has demonstrated to the public of the potential of electric vehicles in terms of reducing fuel consumption and green-house gas from the transport sector. It has brought electric vehicles back into the spotlight worldwide at a moment when fossil fuel prices were reaching unexpected high due to increased demand and strong economic growth. The energy storage capabilities from of fleets of electric vehicles as well as the potentially random discharging and charging offers challenges to the grid in terms of operation and control. Optimal scheduling strategies are key to integrating large numbers of electric vehicles and the smart grid. In this paper, state-of-the-art optimization methods are reviewed on scheduling strategies for the grid integration with electric vehicles. The paper starts with a concise introduction to analytical charging strategies, followed by a review of a number of classical numerical optimization methods, including linear programming, non-linear programming, dynamic programming as well as some other means such as queuing theory. Meta-heuristic techniques are then discussed to deal with the complex, high-dimensional and multi-objective scheduling problem associated with stochastic charging and discharging of electric vehicles. Finally, future research directions are suggested.

Computational methods in the fractional calculus of variations and optimal control

The fractional calculus of variations and fractional optimal control are generalizations of the corresponding classical theories, that allow problem modeling and formulations with arbitrary order derivatives and integrals. Because of the lack of analytic methods to solve such fractional problems, numerical techniques are developed. Here, we mainly investigate the approximation of fractional operators by means of series of integer-order derivatives and generalized finite differences. We give upper bounds for the error of proposed approximations and study their efficiency. Direct and indirect methods in solving fractional variational problems are studied in detail. Furthermore, optimality conditions are discussed for different types of unconstrained and constrained variational problems and for fractional optimal control problems. The introduced numerical methods are employed to solve some illustrative examples.

Substance use and misuse in burn patients: testing the classical hypotheses of the interaction between posttraumatic symptomatology and substance use

Background: We aimed to test whether the three classical hypotheses of the interaction between posttraumatic symptomatology and substance use (high risk of trauma exposure, susceptibility for posttraumatic symptomatology, and self-medication of symptoms), may be useful in the understanding of substance use among burn patients. Methods: We analysed substance use data (nicotine, alcohol, cannabis, amphetamines, cocaine, opiates, and tranquilizers) and psychopathology measures among burn patients admitted to a Burns Unit and enrolled in a longitudinal observational study. Lifetime substance use information (n = 246) was incorporated to analyses aiming to test the high risk hypothesis. Only patients assessed for psychopathology in a six months follow-up (n = 183) were included in prospective analyses testing the susceptibility and self-medication hypotheses. Results: Regarding the high risk hypothesis, results show a higher proportion of heroin and tranquilizer users compared to the general population. Furthermore, in line with the susceptibility hypothesis, higher levels of symptomatology were found in lifetime alcohol, tobacco and drug users during recovery. The self-medication hypothesis could be tested partially due to the hospital stay “cleaning” effect, but severity of symptoms was linked to caffeine, nicotine, alcohol and cannabis use after discharge. Conclusions: We found that the three classical hypotheses could be used to understand the link between traumatic experiences and substance use explaining different patterns of burn patient’s risk for trauma exposure and emergence of symptomatology.

New methods for meta-analysis under a fixed effects framework, with frequentist and Bayesian estimation.

Thesis (Ph.D.)--University of Washington, 2015

Extremum estimators and stochastic optimization methods

Submitted in partial fulfillment for the Requirements for the Degree of PhD in Mathematics, in the Speciality of Statistics in the Faculdade de Ciências e Tecnologia

Meta-heuristic Solution Methods for Rich Vehicle Routing Problems

Le problème de tournées de véhicules (VRP), introduit par Dantzig and Ramser en 1959, est devenu l'un des problèmes les plus étudiés en recherche opérationnelle, et ce, en raison de son intérêt méthodologique et de ses retombées pratiques dans de nombreux domaines tels que le transport, la logistique, les télécommunications et la production. L'objectif général du VRP est d'optimiser l'utilisation des ressources de transport afin de répondre aux besoins des clients tout en respectant les contraintes découlant des exigences du contexte d’application. Les applications réelles du VRP doivent tenir compte d’une grande variété de contraintes et plus ces contraintes sont nombreuse, plus le problème est difficile à résoudre. Les VRPs qui tiennent compte de l’ensemble de ces contraintes rencontrées en pratique et qui se rapprochent des applications réelles forment la classe des problèmes ‘riches’ de tournées de véhicules. Résoudre ces problèmes de manière efficiente pose des défis considérables pour la communauté de chercheurs qui se penchent sur les VRPs. Cette thèse, composée de deux parties, explore certaines extensions du VRP vers ces problèmes. La première partie de cette thèse porte sur le VRP périodique avec des contraintes de fenêtres de temps (PVRPTW). Celui-ci est une extension du VRP classique avec fenêtres de temps (VRPTW) puisqu’il considère un horizon de planification de plusieurs jours pendant lesquels les clients n'ont généralement pas besoin d’être desservi à tous les jours, mais plutôt peuvent être visités selon un certain nombre de combinaisons possibles de jours de livraison. Cette généralisation étend l'éventail d'applications de ce problème à diverses activités de distributions commerciales, telle la collecte des déchets, le balayage des rues, la distribution de produits alimentaires, la livraison du courrier, etc. La principale contribution scientifique de la première partie de cette thèse est le développement d'une méta-heuristique hybride dans la quelle un ensemble de procédures de recherche locales et de méta-heuristiques basées sur les principes de voisinages coopèrent avec un algorithme génétique afin d’améliorer la qualité des solutions et de promouvoir la diversité de la population. Les résultats obtenus montrent que la méthode proposée est très performante et donne de nouvelles meilleures solutions pour certains grands exemplaires du problème. La deuxième partie de cette étude a pour but de présenter, modéliser et résoudre deux problèmes riches de tournées de véhicules, qui sont des extensions du VRPTW en ce sens qu'ils incluent des demandes dépendantes du temps de ramassage et de livraison avec des restrictions au niveau de la synchronization temporelle. Ces problèmes sont connus respectivement sous le nom de Time-dependent Multi-zone Multi-Trip Vehicle Routing Problem with Time Windows (TMZT-VRPTW) et de Multi-zone Mult-Trip Pickup and Delivery Problem with Time Windows and Synchronization (MZT-PDTWS). Ces deux problèmes proviennent de la planification des opérations de systèmes logistiques urbains à deux niveaux. La difficulté de ces problèmes réside dans la manipulation de deux ensembles entrelacés de décisions: la composante des tournées de véhicules qui vise à déterminer les séquences de clients visités par chaque véhicule, et la composante de planification qui vise à faciliter l'arrivée des véhicules selon des restrictions au niveau de la synchronisation temporelle. Auparavant, ces questions ont été abordées séparément. La combinaison de ces types de décisions dans une seule formulation mathématique et dans une même méthode de résolution devrait donc donner de meilleurs résultats que de considérer ces décisions séparément. Dans cette étude, nous proposons des solutions heuristiques qui tiennent compte de ces deux types de décisions simultanément, et ce, d'une manière complète et efficace. Les résultats de tests expérimentaux confirment la performance de la méthode proposée lorsqu’on la compare aux autres méthodes présentées dans la littérature. En effet, la méthode développée propose des solutions nécessitant moins de véhicules et engendrant de moindres frais de déplacement pour effectuer efficacement la même quantité de travail. Dans le contexte des systèmes logistiques urbains, nos résultats impliquent une réduction de la présence de véhicules dans les rues de la ville et, par conséquent, de leur impact négatif sur la congestion et sur l’environnement.

"Statistical Methods in Gear Selectivity and Gear Efficiency Studies”

The preceding discussion and review of literature show that studies on gear selectivity have received great attention, while gear efficiency studies do not seem to have received equal consideration. In temperate waters, fishing industry is well organised and relatively large and well equipped vessels and gear are used for commercial fishing and the number of species are less; whereas in tropics particularly in India, small scale fishery dominates the scene and the fishery is multispecies operated upon by nmltigear. Therefore many of the problems faced in India may not exist in developed countries. Perhaps this would be the reason for the paucity of literature on the problems in estimation of relative efficiency. Much work has been carried out in estimating relative efficiency (Pycha, 1962; Pope, 1963; Gulland, 1967; Dickson, 1971 and Collins, 1979). The main subject of interest in the present thesis is an investigation into the problems in the comparison of fishing gears. especially in using classical test procedures with special reference to the prevailing fishing practices (that is. with reference to the catch data generated by the existing system). This has been taken up with a view to standardizing an approach for comparing the efficiency of fishing gear. Besides this, the implications of the terms ‘gear efficiency‘ and ‘gear selectivity‘ have been examined and based on the commonly used selectivity model (Holt, 1963), estimation of the ratio of fishing power of two gear has been considered. An attempt to determine the size of fish for which a gear is most efficient.has also been made. The work has been presented in eight chapters