Estudio contrastivo de transposición semántica entre el lenguaje metafórico en lengua inglesa y española

El projecte de tesi doctoral que estem portant a terme requereix una mitjana de quatre anys de durada. A hores d‟ara, nou mesos després de la concessió de l‟ajut, estem treballant per a la defensa del projecte, que farem en el primer trimestre de l‟any 2012. El nostre treball pertany al camp de la lingüística i està directament relacionat amb la lexicografia i la semàntica. L‟objectiu final és el disseny de materials per a la traducció i l‟ensenyament de llengües. L‟ús de lèxic és el tema escollit. D‟una banda, volem esbrinar com autors consagrats de literatura utilitzen el llenguatge. Per això, mirem de diferenciar el que es consideran usos “normals” del llenguatge del que serien “explotacions”, especialmente aquelles relacionades amb l‟extensió de significat i, més específicament, amb la metáfora. D‟altra banda, perseguim fer una proposta de material destinat tant a l‟ensenyament de llengües estrangeres com a la traducció (els idiomas amb els quals treballem són anglès i espanyol). Les teories que utilitzem en la nostra recerca són la teoria del lèxic generatiu (de J. Pustejovsky) i la teoria de normes i explotacions (de P. Hanks). Encara no hem decidit quins autors estudiarem, tot i estar consultant obres d‟escriptors com V. S. Naipaul i J. Marías. El treball de recerca desenvolupat fins avui ha consistit en la redacció de la memòria final de màster (Màster Oficial en Formació de Professors d‟Espanyol com a Llengua Estrangera) en què s‟estudiava el tractament de la metáfora en diferents diccionaris d‟ELE i d‟EFL i en la cerca, lectura i selección de documents que podran ajudar-nos en la nostra empresa.

Sobre els mapes de semblança quàntica molecular

Partint de les definicions usuals de Mesures de Semblança Quàntica (MSQ), es considera la dependència d'aquestes mesures respecte de la superposició molecular. Pel cas particular en qnè els sistemes comparats siguin una molècula i un Àtom i que les mesures es calculin amb l'aproximació EASA, les MSQ esdevenen funcions de les tres coordenades de l'espai. Mantenint fixa una de les tres coordenades, es pot representar fàcilment la variació del valor de semblança en un pla determinat, i obtenir els anomenats mapes de semblança. En aquest article, es comparen els mapes de semblança obtinguts amb diferents MSQ per a sistemes senzills

Sobre les relacions lineals d'energia lliure: mesures de semblança molecular quàntica sobre funcions de densitat electrònica modificad

En aquest treball es presenta l'ús de funcions de densitat electrònica de forat de Fermi per incrementar el paper que pren una regió molecular concreta, considerada com a responsable de la reactivitat molecular, tot i mantenir la mida de la funció de densitat original. Aquestes densitats s'utilitzen per fer mesures d'autosemblança molecular quàntica i es presenten com una alternativa a l'ús de fragments moleculars aillats en estudis de relació entre estructura i propietat. El treball es complementa amb un exemple pràctic, on es correlaciona l'autosemblanca molecular a partir de densitats modificades amb l'energia d'una reacció isodòsmica

International regimes as knowledge syndicates? Energy and trends of global governance

El poder de l'Estat i la sobirania tradicional s'està deteriorant de manera constant, sobretot en termes de la provisió de certs béns públics fonamentals. Els Estats, en particular, són incapaços de manejar el coneixement i la informació que és essencial per mantenir la competitivitat i la sostenibilitat en una economia interdependent. Estructures fiables de la governança mundial i la cooperació internacional estan lluny de ser establertes. Energia com a problema a les agendes p dels governs, les empreses privades i la societat civil és un exemple manifest d'aquesta dinàmica.. L'actual sistema de governança mundial d'energia implica accions polítiques disperses per actors divers. L'Agència Internacional de l'Energia té un paper destacat, però està debilitat per la seva composició limitada i basada en el coneixement- epistèmic en lloc del material o executiu. Aquest treball sosté que ni la mida ni nombre de membres disponibles estan dificultant la governabilitat mundial d'energia. Més aviat, l'energia és una sèrie de béns públics que es troben als llimbs, on els estats no poden pagar la seva disposició, així com els diversos interessos impedir l'establiment d'una autoritat internacional. Després de la introducció de la teoria del règim internacional i el concepte de coneixement basats en les comunitats epistèmiques, l'article revisa l'estat actual de la governabilitat de l'energia mundia. A continuació es presenta una comparació d'aquesta estructura amb els règims de govern nacional i regional, d'una banda, i amb règims globals ambientals i de salut, de l'altra

Detecció automàtica de punts facials característics utilitzant Random Ferns i el criteri de la información mútua simplificada

En aquest article comparem el rendiment que presenten dos sistemes de reconeixement de punts característics en imatges: en el primer utilitzem la tècnica Random Ferns bàsica i en el segon (que anomenem Ferns amb Informació Mútua o FIM) apliquem una tècnica d'obtenció de Ferns utilitzant un criteri simplificat de la informació mútua.

Full Exploration of the Diels–Alder Cycloaddition on Metallofullerenes M3N@C80 (M=Sc, Lu, Gd): The D5h versus Ih Isomer and the Influence of the Metal Cluster

In this work a detailed investigation of the exohedral reactivity of the most important and abundant endohedral metallofullerene (EMF) is provided, that is, Sc3N@Ih-C80 and its D5h counterpart Sc3N@D5h-C80, and the (bio)chemically relevant lutetium- and gadolinium-based M3N@Ih/D5h-C80 EMFs (M=Sc, Lu, Gd). In particular, we analyze the thermodynamics and kinetics of the Diels–Alder cycloaddition of s-cis-1,3-butadiene on all the different bonds of the Ih-C80 and D5h-C80 cages and their endohedral derivatives. First, we discuss the thermodynamic and kinetic aspects of the cycloaddition reaction on the hollow fullerenes and the two isomers of Sc3N@C80. Afterwards, the effect of the nature of the metal nitride is analyzed in detail. In general, our BP86/TZP//BP86/DZP calculations indicate that [5,6] bonds are more reactive than [6,6] bonds for the two isomers. The [5,6] bond D5h-b, which is the most similar to the unique [5,6] bond type in the icosahedral cage, Ih-a, is the most reactive bond in M3N@D5h-C80 regardless of M. Sc3N@C80 and Lu3N@C80 give similar results; the regioselectivity is, however, significantly reduced for the larger and more electropositive M=Gd, as previously found in similar metallofullerenes. Calculations also show that the D5h isomer is more reactive from the kinetic point of view than the Ih one in all cases which is in good agreement with experiments

Negative Fukui functions: new insights based on electronegativity equalization

The occurrence of negative values for Fukui functions was studied through the electronegativity equalization method. Using algebraic relations between Fukui functions and different other conceptual DFT quantities on the one hand and the hardness matrix on the other hand, expressions were obtained for Fukui functions for several archetypical small molecules. Based on EEM calculations for large molecular sets, no negative Fukui functions were found

Critical thoughts on computing atom condensed Fukui functions

Different procedures to obtain atom condensed Fukui functions are described. It is shown how the resulting values may differ depending on the exact approach to atom condensed Fukui functions. The condensed Fukui function can be computed using either the fragment of molecular response approach or the response of molecular fragment approach. The two approaches are nonequivalent; only the latter approach corresponds in general with a population difference expression. The Mulliken approach does not depend on the approach taken but has some computational drawbacks. The different resulting expressions are tested for a wide set of molecules. In practice one must make seemingly arbitrary choices about how to compute condensed Fukui functions, which suggests questioning the role of these indicators in conceptual density-functional theory

The mapping of the local contributions of Fermi and Coulomb correlation into intracule and extracule density distributions

The contributions of the correlated and uncorrelated components of the electron-pair density to atomic and molecular intracule I(r) and extracule E(R) densities and its Laplacian functions ∇2I(r) and ∇2E(R) are analyzed at the Hartree-Fock (HF) and configuration interaction (CI) levels of theory. The topologies of the uncorrelated components of these functions can be rationalized in terms of the corresponding one-electron densities. In contrast, by analyzing the correlated components of I(r) and E(R), namely, IC(r) and EC(R), the effect of electron Fermi and Coulomb correlation can be assessed at the HF and CI levels of theory. Moreover, the contribution of Coulomb correlation can be isolated by means of difference maps between IC(r) and EC(R) distributions calculated at the two levels of theory. As application examples, the He, Ne, and Ar atomic series, the C2-2, N2, O2+2 molecular series, and the C2H4 molecule have been investigated. For these atoms and molecules, it is found that Fermi correlation accounts for the main characteristics of IC(r) and EC(R), with Coulomb correlation increasing slightly the locality of these functions at the CI level of theory. Furthermore, IC(r), EC(R), and the associated Laplacian functions, reveal the short-ranged nature and high isotropy of Fermi and Coulomb correlation in atoms and molecules

The relevance of the Laplacian of intracule and extracule density distributions for analyzing electron-electron interactions in molecules

A topological analysis of intracule and extracule densities and their Laplacians computed within the Hartree-Fock approximation is presented. The analysis of the density distributions reveals that among all possible electron-electron interactions in atoms and between atoms in molecules only very few are located rigorously as local maxima. In contrast, they are clearly identified as local minima in the topology of Laplacian maps. The conceptually different interpretation of intracule and extracule maps is also discussed in detail. An application example to the C2H2, C2H4, and C2H6 series of molecules is presented

A new efficient approach to the direct restricted active space self-consistent field method

An implicitly parallel method for integral-block driven restricted active space self-consistent field (RASSCF) algorithms is presented. The approach is based on a model space representation of the RAS active orbitals with an efficient expansion of the model subspaces. The applicability of the method is demonstrated with a RASSCF investigation of the first two excited states of indole

Automatic generation of active coordinates for quantum dynamics calculations: application to the dynamics of benzene photochemistry

A new practical method to generate a subspace of active coordinates for quantum dynamics calculations is presented. These reduced coordinates are obtained as the normal modes of an analytical quadratic representation of the energy difference between excited and ground states within the complete active space self-consistent field method. At the Franck-Condon point, the largest negative eigenvalues of this Hessian correspond to the photoactive modes: those that reduce the energy difference and lead to the conical intersection; eigenvalues close to 0 correspond to bath modes, while modes with large positive eigenvalues are photoinactive vibrations, which increase the energy difference. The efficacy of quantum dynamics run in the subspace of the photoactive modes is illustrated with the photochemistry of benzene, where theoretical simulations are designed to assist optimal control experiments

Nuclear magnetic resonance chemical shifts with the statistical average of orbital-dependent model potentials in Kohn-Sham density functional theory

The performance of the SAOP potential for the calculation of NMR chemical shifts was evaluated. SAOP results show considerable improvement with respect to previous potentials, like VWN or BP86, at least for the carbon, nitrogen, oxygen, and fluorine chemical shifts. Furthermore, a few NMR calculations carried out on third period atoms (S, P, and Cl) improved when using the SAOP potential

Energy partitioning for "fuzzy" atoms

The total energy of molecule in terms of 'fuzzy atoms' presented as sum of one- and two-atomic energy components is described. The divisions of three-dimensional physical space into atomic regions exhibit continuous transition from one to another. The energy components are on chemical energy scale according to proper definitions. The Becke's integration scheme and weight function determines realization of method which permits effective numerical integrations

C-H···O H-bonded complexes: how does basis set superposition error change their potential-energy surfaces?

Geometries, vibrational frequencies, and interaction energies of the CNH⋯O3 and HCCH⋯O3 complexes are calculated in a counterpoise-corrected (CP-corrected) potential-energy surface (PES) that corrects for the basis set superposition error (BSSE). Ab initio calculations are performed at the Hartree-Fock (HF) and second-order Møller-Plesset (MP2) levels, using the 6-31G(d,p) and D95++(d,p) basis sets. Interaction energies are presented including corrections for zero-point vibrational energy (ZPVE) and thermal correction to enthalpy at 298 K. The CP-corrected and conventional PES are compared; the unconnected PES obtained using the larger basis set including diffuse functions exhibits a double well shape, whereas use of the 6-31G(d,p) basis set leads to a flat single-well profile. The CP-corrected PES has always a multiple-well shape. In particular, it is shown that the CP-corrected PES using the smaller basis set is qualitatively analogous to that obtained with the larger basis sets, so the CP method becomes useful to correctly describe large systems, where the use of small basis sets may be necessary