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.

Interaccions moleculars: correcció de l'error de superposició de base i propietat de les funcions flotants

A primary interest of this thesis is to obtain a powerful tool for determining structural properties, electrical and reactivity of molecules. A second interest is the study of fundamental error based on complex overlay of bridge hydrogen. One way to correct this error, using Counterpoise correction proposed by Boys and Bernardi. Usually the Counterpoise correction is applied promptly on the geometries previously optimized. Our goal was to find areas of potential which had all the points fixed with CP. These surfaces have a minimum corresponding to a surface other than corrected, ie, the geometric parameters will be different. The curvature of this minimum will also be different, therefore the vibrational frequency will also change when they are corrected with BSSE. Once constructed these surfaces have been studied various complex. It has also been investigated as the method for calculating the error influenced on the basis superposition.

Building the Directorate General for Urban Affairs in European Union. A proposal for the European Commission

The present documents get together reflection elements that allow sustaining the irreversibility of the process that leads to the creation of a Directorate General for Urban AffairsThe irreversibility of this process results of the assumed necessity to implement the cooperation between Member-States in respect to the urban and territorial development policy. It is time, with vision, to assume the urgency to create, as well, in this area an European joint policy and which are the necessary structures for its definition and implementation within the EU framework. O Directorate General for Urban Affairs deverá articular-se em particular com o Comité Económico e Social e com o Comité das RegiõesThe present text is based essentially on political documents on urban and territorial affairs elaborated in the extent of the EU and in the general guideline documents produced by the EU, which favor social, economic and territorial integration.

El error como causa de inculpabilidad en el ilícito tributario

El artículo 342 del Código Tributario, al hablar de los elementos constitutivos de los ilícitos tributarios, establece que es necesaria la presencia de dolo o culpa rechazando la responsabilidad objetiva, que si acepta para contravenciones o faltas reglamentarias, es decir la culpabilidad como elemento del delito tributario es reconocida, lo cual lleva a que el artículo 338 del Código Tributario, reconozca al error como una circunstancia que excluye la responsabilidad penal tributaria, pero no existe desarrollo sobre el contenido del precepto. Esta falta de explicación obliga a recurrir al desarrollo que se ha dado sobre el tema por otras ramas del derecho, así se analizan las explicaciones realizadas por el Derecho Constitucional y el Derecho Penal, siendo este último donde más desarrollo se ha dado sobre el tema, sin poder olvidar la importancia de los derechos fundamentales de la persona. La presente tesis busca aportar criterios que sean útiles y aplicables en el campo tributario, para lo cual se tratará los siguientes temas: Derecho Penal Administrativo, naturaleza de las infracciones tributarias: Derecho Penal aplicable al campo tributario, la culpabilidad en Tratados Internacionales sobre derechos humanos, principio de culpabilidad y sus elementos, error como eximente de responsabilidad, límites de la presencia del error y elusión tributaria.

El error judicial inexcusable en el Estado constitucional de derechos y justicia

Esta investigación estudia el rol del juez en el Estado constitucional de derechos y justicia en el Ecuador, el error inexcusable y el procesamiento disciplinario por error judicial inexcusable desde sus principios de legalidad y taxatividad, la etiología del error, el órgano competente y la independencia judicial. Presenta conclusiones y recomendaciones.