TU Graz: Course: 707.000 Web Science and Web Technology: Lecture 3: Network Theory and Terminology

In this class, we will discuss network theory fundamentals, including concepts such as diameter, distance, clustering coefficient and others. We will also discuss different types of networks, such as scale-free networks, random networks etc. Readings: Graph structure in the Web, A. Broder and R. Kumar and F. Maghoul and P. Raghavan and S. Rajagopalan and R. Stata and A. Tomkins and J. Wiener Computer Networks 33 309--320 (2000) [Web link, Alternative Link] Optional: The Structure and Function of Complex Networks, M.E.J. Newman, SIAM Review 45 167--256 (2003) [Web link] Original course at: http://kmi.tugraz.at/staff/markus/courses/SS2008/707.000_web-science/

Aplicación de colas de Poisson en procesos de ‘toma de decisiones’ en la gestión de servicios médicos

En este documento se revisa teóricamente la distribución de probabilidad de Poisson como función que asigna a cada suceso definido, sobre una variable aleatoria discreta, la probabilidad de ocurrencia en un intervalo de tiempo o región del espacio disjunto. Adicionalmente se revisa la distribución exponencial negativa empleada para modelar el intervalo de tiempo entre eventos consecutivos de Poisson que ocurren de manera independiente; es decir, en los cuales la probabilidad de ocurrencia de los eventos sucedidos en un intervalo de tiempo no depende de los ocurridos en otros intervalos de tiempo, por esta razón se afirma que es una distribución que no tiene memoria. El proceso de Poisson relaciona la función de Poisson, que representa un conjunto de eventos independientes sucedidos en un intervalo de tiempo o región del espacio con los tiempos dados entre la ocurrencia de los eventos según la distribución exponencial negativa. Los anteriores conceptos se usan en la teoría de colas, rama de la investigación de operaciones que describe y brinda soluciones a situaciones en las que un conjunto de individuos o elementos forman colas en espera de que se les preste un servicio, por lo cual se presentan ejemplos de aplicación en el ámbito médico.

Conceptuals Mentefactos as a Didactic-Pedagogical Strategy of the Basic Concepts in the Sampling Theory Applyed to the Health Research

In populational sampling it is vitally important to clarify and discern: first, the design or sampling method used to solve the research problem; second, the sampling size, taking into account different components (precision, reliability, variance); third, random selection and fourth, the precision estimate (sampling errors), so as to determine if it is possible to infer the obtained estimates from the target population. The existing difficulty to use concepts from the sampling theory is to understand them with absolute clarity and, to achieve it, the help from didactic-pedagogical strategies arranged as conceptual “mentefactos” (simple hierarchic diagrams organized from propositions) may prove useful. This paper presents the conceptual definition, through conceptual “mentefactos”, of the most important populational probabilistic sampling concepts, in order to obtain representative samples from populations in health research.

Análisis al Proceso de Titulación Minera en Colombia desde TOC (Theory Of Constraints)

El incumplimiento reiterado de la normatividad y políticas relacionadas con los tiempos de respuesta del proceso de contratación minera del país, desarrollado actualmente por la recién creada Agencia Nacional de Minería ANM, ha suscitado que la administración del recurso minero no se realice bajo los principios de eficiencia, eficacia, economía y celeridad. Estas debilidades manifiestas provocan represamientos en la resolución de trámites, congelación de áreas para contratar, sobrecostos, demoras en los tiempos de respuesta establecidos por la normatividad vigente y trae como consecuencia incertidumbre en los inversionistas mineros y pérdidas por concepto de recaudo de canon superficiario, entre otras. El objetivo del presente trabajo de investigación consiste en analizar el proceso de titulación minera de Colombia a partir de la filosofía de mejora continua desarrollado en la teoría de restricciones TOC (Theory Of Constraints), para poder identificar cuáles son los cuellos de botella que no permiten que el proceso fluya de manera adecuada y proponer alternativas de mejora, que con su implementación exploten y subordinen la limitaciones al sistema.

Random walk radiosity with generalized absorption probabilities

The author studies random walk estimators for radiosity with generalized absorption probabilities. That is, a path will either die or survive on a patch according to an arbitrary probability. The estimators studied so far, the infinite path length estimator and finite path length one, can be considered as particular cases. Practical applications of the random walks with generalized probabilities are given. A necessary and sufficient condition for the existence of the variance is given, together with heuristics to be used in practical cases. The optimal probabilities are also found for the case when one is interested in the whole scene, and are equal to the reflectivities

Basis set superposition error-counterpoise corrected potential energy surfaces : application to hydrogen peroxide ... X (X=F-, Cl-, Br-, Li+, Na+) complexes

Møller-Plesset (MP2) and Becke-3-Lee-Yang-Parr (B3LYP) calculations have been used to compare the geometrical parameters, hydrogen-bonding properties, vibrational frequencies and relative energies for several X- and X+ hydrogen peroxide complexes. The geometries and interaction energies were corrected for the basis set superposition error (BSSE) in all the complexes (1-5), using the full counterpoise method, yielding small BSSE values for the 6-311 + G(3df,2p) basis set used. The interaction energies calculated ranged from medium to strong hydrogen-bonding systems (1-3) and strong electrostatic interactions (4 and 5). The molecular interactions have been characterized using the atoms in molecules theory (AIM), and by the analysis of the vibrational frequencies. The minima on the BSSE-counterpoise corrected potential-energy surface (PES) have been determined as described by S. Simón, M. Duran, and J. J. Dannenberg, and the results were compared with the uncorrected PES

A chemical Hamiltonian approach study of the basis set superposition error changes on electron densities and one- and two-center energy components

A comparision of the local effects of the basis set superposition error (BSSE) on the electron densities and energy components of three representative H-bonded complexes was carried out. The electron densities were obtained with Hartee-Fock and density functional theory versions of the chemical Hamiltonian approach (CHA) methodology. It was shown that the effects of the BSSE were common for all complexes studied. The electron density difference maps and the chemical energy component analysis (CECA) analysis confirmed that the local effects of the BSSE were different when diffuse functions were present in the calculations

A quantum molecular similarity analysis of changes in molecular electron density caused by basis set flotation and electric field application

Quantum molecular similarity (QMS) techniques are used to assess the response of the electron density of various small molecules to application of a static, uniform electric field. Likewise, QMS is used to analyze the changes in electron density generated by the process of floating a basis set. The results obtained show an interrelation between the floating process, the optimum geometry, and the presence of an external field. Cases involving the Le Chatelier principle are discussed, and an insight on the changes of bond critical point properties, self-similarity values and density differences is performed

Ab initio benchmark study for the oxidative addition of CH4 to Pd: importance of basis-set flexibility and polarization

To obtain a state-of-the-art benchmark potential energy surface (PES) for the archetypal oxidative addition of the methane C-H bond to the palladium atom, we have explored this PES using a hierarchical series of ab initio methods (Hartree-Fock, second-order Møller-Plesset perturbation theory, fourth-order Møller-Plesset perturbation theory with single, double and quadruple excitations, coupled cluster theory with single and double excitations (CCSD), and with triple excitations treated perturbatively [CCSD(T)]) and hybrid density functional theory using the B3LYP functional, in combination with a hierarchical series of ten Gaussian-type basis sets, up to g polarization. Relativistic effects are taken into account either through a relativistic effective core potential for palladium or through a full four-component all-electron approach. Counterpoise corrected relative energies of stationary points are converged to within 0.1-0.2 kcal/mol as a function of the basis-set size. Our best estimate of kinetic and thermodynamic parameters is -8.1 (-8.3) kcal/mol for the formation of the reactant complex, 5.8 (3.1) kcal/mol for the activation energy relative to the separate reactants, and 0.8 (-1.2) kcal/mol for the reaction energy (zero-point vibrational energy-corrected values in parentheses). This agrees well with available experimental data. Our work highlights the importance of sufficient higher angular momentum polarization functions, f and g, for correctly describing metal-d-electron correlation and, thus, for obtaining reliable relative energies. We show that standard basis sets, such as LANL2DZ+ 1f for palladium, are not sufficiently polarized for this purpose and lead to erroneous CCSD(T) results. B3LYP is associated with smaller basis set superposition errors and shows faster convergence with basis-set size but yields relative energies (in particular, a reaction barrier) that are ca. 3.5 kcal/mol higher than the corresponding CCSD(T) values

Modelización constitutiva y computacional del daño y la fractura de materiales compuestos

En el trabajo se definen modelos constitutivos que permiten reproducir el proceso de fallo de estructuras de materiales compuestos en distintas escalas bajo cargas estáticas. Se define un modelo constitutivo para determinar la respuesta de estructuras de materiales compuestos mediante la teoría de laminados. El modelo es validado mediante un programa de ensayos experimentales con probetas con un agujero central geométricamente similares. Se muestra la capacidad del modelo de detectar el efecto tamaño. Se define un modelo constitutivo para materiales transversalmente isótropos bajo estados tridimensionales de tensión. El modelo se valida analizando numéricamente el proceso de agrietamiento de la matriz. Finalmente se desarrolla un modelo analítico para determinar el agrietamiento de la matriz y la delaminación entre las capas.

Implementation and application of basis set superposition error-correction schemes to the theoretical modeling of weak intermolecular interactions

This thesis deals with the so-called Basis Set Superposition Error (BSSE) from both a methodological and a practical point of view. The purpose of the present thesis is twofold: (a) to contribute step ahead in the correct characterization of weakly bound complexes and, (b) to shed light the understanding of the actual implications of the basis set extension effects in the ab intio calculations and contribute to the BSSE debate. The existing BSSE-correction procedures are deeply analyzed, compared, validated and, if necessary, improved. A new interpretation of the counterpoise (CP) method is used in order to define counterpoise-corrected descriptions of the molecular complexes. This novel point of view allows for a study of the BSSE-effects not only in the interaction energy but also on the potential energy surface and, in general, in any property derived from the molecular energy and its derivatives A program has been developed for the calculation of CP-corrected geometry optimizations and vibrational frequencies, also using several counterpoise schemes for the case of molecular clusters. The method has also been implemented in Gaussian98 revA10 package. The Chemical Hamiltonian Approach (CHA) methodology has been also implemented at the RHF and UHF levels of theory for an arbitrary number interacting systems using an algorithm based on block-diagonal matrices. Along with the methodological development, the effects of the BSSE on the properties of molecular complexes have been discussed in detail. The CP and CHA methodologies are used for the determination of BSSE-corrected molecular complexes properties related to the Potential Energy Surfaces and molecular wavefunction, respectively. First, the behaviour of both BSSE-correction schemes are systematically compared at different levels of theory and basis sets for a number of hydrogen-bonded complexes. The Complete Basis Set (CBS) limit of both uncorrected and CP-corrected molecular properties like stabilization energies and intermolecular distances has also been determined, showing the capital importance of the BSSE correction. Several controversial topics of the BSSE correction are addressed as well. The application of the counterpoise method is applied to internal rotational barriers. The importance of the nuclear relaxation term is also pointed out. The viability of the CP method for dealing with charged complexes and the BSSE effects on the double-well PES blue-shifted hydrogen bonds is also studied in detail. In the case of the molecular clusters the effect of high-order BSSE effects introduced with the hierarchical counterpoise scheme is also determined. The effect of the BSSE on the electron density-related properties is also addressed. The first-order electron density obtained with the CHA/F and CHA/DFT methodologies was used to assess, both graphically and numerically, the redistribution of the charge density upon BSSE-correction. Several tools like the Atoms in Molecules topologycal analysis, density difference maps, Quantum Molecular Similarity, and Chemical Energy Component Analysis were used to deeply analyze, for the first time, the BSSE effects on the electron density of several hydrogen bonded complexes of increasing size. The indirect effect of the BSSE on intermolecular perturbation theory results is also pointed out It is shown that for a BSSE-free SAPT study of hydrogen fluoride clusters, the use of a counterpoise-corrected PES is essential in order to determine the proper molecular geometry to perform the SAPT analysis.

Water wave scattering by finite arrays of circular structures

The scattering of small amplitude water waves by a finite array of locally axisymmetric structures is considered. Regions of varying quiescent depth are included and their axisymmetric nature, together with a mild-slope approximation, permits an adaptation of well-known interaction theory which ultimately reduces the problem to a simple numerical calculation. Numerical results are given and effects due to regions of varying depth on wave loading and free-surface elevation are presented.

Boundary integral equations on unbounded rough surfaces: Fredholmness and the finite section method

We consider a class of boundary integral equations that arise in the study of strongly elliptic BVPs in unbounded domains of the form $D = \{(x, z)\in \mathbb{R}^{n+1} : x\in \mathbb{R}^n, z > f(x)\}$ where $f : \mathbb{R}^n \to\mathbb{R}$ is a sufficiently smooth bounded and continuous function. A number of specific problems of this type, for example acoustic scattering problems, problems involving elastic waves, and problems in potential theory, have been reformulated as second kind integral equations $u+Ku = v$ in the space $BC$ of bounded, continuous functions. Having recourse to the so-called limit operator method, we address two questions for the operator $A = I + K$ under consideration, with an emphasis on the function space setting $BC$. Firstly, under which conditions is $A$ a Fredholm operator, and, secondly, when is the finite section method applicable to $A$?

Force constants and dipole moment derivatives of molecules from perturbed Hartree-Fock calculations II. Applications to limited basis set SCF-MO wavefunctions

The perturbed Hartree–Fock theory developed in the preceding paper is applied to LiH, BH, and HF, using limited basis‐set SCF–MO wavefunctions derived by previous workers. The calculated values for the force constant ke and the dipole‐moment derivative μ(1) are (experimental values in parentheses): LiH, ke  =  1.618(1.026)mdyn/Å,μ(1)  =  −18.77(−2.0±0.3)D/ÅBH,ke  =  5.199(3.032)mdyn/Å,μ(1)  =  −1.03(−)D/Å;HF,ke  =  12.90(9.651)mdyn/Å,μ(1)  =  −2.15(+1.50)D/Å. The values of the force on the proton were calculated exactly and according to the Hellmann–Feynman theorem in each case, and the discrepancies show that none of the wavefunctions used are close to the Hartree–Fock limit, so that the large errors in ke and μ(1) are not surprising. However no difficulties arose in the perturbed Hartree–Fock calculation, so that the application of the theory to more accurate wavefunctions appears quite feasible.

ASYM20: a program for force constant and normal coordinate calculations, with a critical review of the theory involved

The theory of harmonic force constant refinement calculations is reviewed, and a general-purpose program for force constant and normal coordinate calculations is described. The program, called ASYM20. is available through Quantum Chemistry Program Exchange. It will work on molecules of any symmetry containing up to 20 atoms and will produce results on a series of isotopomers as desired. The vibrational secular equations are solved in either nonredundant valence internal coordinates or symmetry coordinates. As well as calculating the (harmonic) vibrational wavenumbers and normal coordinates, the program will calculate centrifugal distortion constants, Coriolis zeta constants, harmonic contributions to the α′s. root-mean-square amplitudes of vibration, and other quantities related to gas electron-diffraction studies and thermodynamic properties. The program will work in either a predict mode, in which it calculates results from an input force field, or in a refine mode, in which it refines an input force field by least squares to fit observed data on the quantities mentioned above. Predicate values of the force constants may be included in the data set for a least-squares refinement. The program is written in FORTRAN for use on a PC or a mainframe computer. Operation is mainly controlled by steering indices in the input data file, but some interactive control is also implemented.