Exploring chromium (VI) dioxodihalides chemistry: is density functional theory the most suitable tool?

A comparative systematic study of the CrO2F2 compound has been performed using different conventional ab initio methodologies and density functional procedures. Two points have been analyzed: first, the accuracy of results yielded by each method under study, and second, the computational cost required to reach such results. Weighing up both aspects, density functional theory has been found to be more appropriate than the Hartree-Fock (HF) and the analyzed post-HF methods. Hence, the structural characterization and spectroscopic elucidation of the full CrO2X2 series (X=F,Cl,Br,I) has been done at this level of theory. Emphasis has been given to the unknown CrO2I2 species, and specially to the UV/visible spectra of all four compounds. Furthermore, a topological analysis in terms of charge density distributions has revealed why the valence shell electron pair repulsion model fails in predicting the molecular shape of such CrO2X2 complexes

The hardness profile as a tool to detect spurious stationary points in the potential energy surface

The energy and hardness profile for a series of inter and intramolecular conformational changes at several levels of calculation were computed. The hardness profiles were found to be calculated as the difference between the vertical ionization potential and electron affinity. The hardness profile shows the correct number of stationary points independently of the basis set and methodology used. It was found that the hardness profiles can be used to check the reliability of the energy profiles for those chemical system

Are the maximum hardness and minimum polarizability principles always obeyed in nontotally symmetric vibrations?

An overview is given on a study which showed that not only in chemical reactions but also in the favorable case of nontotally symmetric vibrations where the chemical and external potentials keep approximately constant, the generalized maximum hardness principle (GMHP) and generalized minimum polarizability principle (GMPP) may not be obeyed. A method that allows an accurate determination of the nontotally symmetric molecular distortions with more marked GMPP or anti-GMPP character through diagonalization of the polarizability Hessian matrix is introduced

Relations among several nuclear and electronic density functional reactivity indexes

A set of connections among several nuclear and electronic indexes of reactivity in the framework of the conceptual Density Functional Theory by using an expansion ofthe energy functional in terms of the total number of electrons and the normal coordinates within a canonical ensemble was derived. The relations obtained provided explicit links between important quantities related to the chemical reactivity of a system. This paper particularly demonstrates that the derivative of the electronic energy with respect to the external potential of a system in its equilibrium geometry was equal to the negative of the nuclear repulsion derivative with respect to the external potential

Variational calculation of vibrational linear and nonlinear optical properties

A variational approach for reliably calculating vibrational linear and nonlinear optical properties of molecules with large electrical and/or mechanical anharmonicity is introduced. This approach utilizes a self-consistent solution of the vibrational Schrödinger equation for the complete field-dependent potential-energy surface and, then, adds higher-level vibrational correlation corrections as desired. An initial application is made to static properties for three molecules of widely varying anharmonicity using the lowest-level vibrational correlation treatment (i.e., vibrational Møller-Plesset perturbation theory). Our results indicate when the conventional Bishop-Kirtman perturbation method can be expected to break down and when high-level vibrational correlation methods are likely to be required. Future improvements and extensions are discussed

Basis set and electron correlation effects on initial convergence for vibrational nonlinear optical properties of conjugated organic molecules

The level of ab initio theory which is necessary to compute reliable values for the static and dynamic (hyper)polarizabilities of three medium size π-conjugated organic nonlinear optical (NLO) molecules is investigated. With the employment of field-induced coordinates in combination with a finite field procedure, the calculations were made possible. It is stated that to obtain reasonable values for the various individual contributions to the (hyper)polarizability, it is necessary to include electron correlation. Based on the results, the convergence of the usual perturbation treatment for vibrational anharmonicity was examined

Initial convergence of the perturbation series expansion for vibrational nonlinear optical properties

Initial convergence of the perturbation series expansion for vibrational nonlinear optical (NLO) properties was analyzed. The zero-point vibrational average (ZPVA) was obtained through first-order in mechanical plus electrical anharmonicity. Results indicated that higher-order terms in electrical and mechanical anharmonicity can make substantial contributions to the pure vibrational polarizibility of typical NLO molecules

Knowledge management for systems biology a general and visually driven framework applied to translational medicine

Background: To enhance our understanding of complex biological systems like diseases we need to put all of the available data into context and use this to detect relations, pattern and rules which allow predictive hypotheses to be defined. Life science has become a data rich science with information about the behaviour of millions of entities like genes, chemical compounds, diseases, cell types and organs, which are organised in many different databases and/or spread throughout the literature. Existing knowledge such as genotype - phenotype relations or signal transduction pathways must be semantically integrated and dynamically organised into structured networks that are connected with clinical and experimental data. Different approaches to this challenge exist but so far none has proven entirely satisfactory. Results: To address this challenge we previously developed a generic knowledge management framework, BioXM™, which allows the dynamic, graphic generation of domain specific knowledge representation models based on specific objects and their relations supporting annotations and ontologies. Here we demonstrate the utility of BioXM for knowledge management in systems biology as part of the EU FP6 BioBridge project on translational approaches to chronic diseases. From clinical and experimental data, text-mining results and public databases we generate a chronic obstructive pulmonary disease (COPD) knowledge base and demonstrate its use by mining specific molecular networks together with integrated clinical and experimental data. Conclusions: We generate the first semantically integrated COPD specific public knowledge base and find that for the integration of clinical and experimental data with pre-existing knowledge the configuration based set-up enabled by BioXM reduced implementation time and effort for the knowledge base compared to similar systems implemented as classical software development projects. The knowledgebase enables the retrieval of sub-networks including protein-protein interaction, pathway, gene - disease and gene - compound data which are used for subsequent data analysis, modelling and simulation. Pre-structured queries and reports enhance usability; establishing their use in everyday clinical settings requires further simplification with a browser based interface which is currently under development.

WikiSAC: sistema col·laboratiu per a l’ atenció ciutadana en administracions municipals

L’objectiu dels Serveis Intel·ligents d’Atenció Ciutadana (SAC) és donar resposta a les necessitats d'informació dels ciutadans sobre els serveis i les actuacions del municipi i, per extensió, del conjunt del serveis d'interès ciutadà. Des que l’ iSAC s’ha posat en funcionament, periòdicament s’analitzen les consultes que es fan en el sistema i el grau de satisfacció que la ciutadania té d’aquest servei. Tot i que en general les valoracions són satisfactòries s’ha observat que actualment aquest sistema té un buit, hi ha un ampli ventall de respostes que, de moment, l’iSAC no és capaç de resoldre, i possiblement el 010, el call center del servei d’atenció ciutadana, tampoc. Algunes de les cerques realitzades marxen molt de l’àmbit municipal i és l’experiència de la mateixa ciutadania la que pot oferir un millor resultat. És per aquest motiu que ha sorgit la necessitat de crear wikiSAC. Eina que te com a principals objectius que: poder crear, modificar i eliminar el contingut d’una pàgina de forma interactiva de manera fàcil i ràpida a través d’un navegador web; controlar els continguts ofensius i malintencionats; conservar un historial de canvis; incentivar la participació ciutadana i aconseguir que aquest sigui un lloc on els ciutadans preguntin, suggereixin i opinin sobre temes relacionats amb el seu municipi i aconseguir que els ciutadans es sentin més integrats amb el funcionament de l’administració, col∙laborant en les tasques d’informació i atenció ciutadana

L'Ansietat dels estudiants davant el pràcticum: és necessari intervenir?

L’objectiu d’aquesta recerca és realitzar un estudi exploratori amb la finalitat d’avaluarl’ansietat percebuda pels estudiants immediatament abans de començar el Pràcticum encentres externs, la contribució de les creences disfuncionals a la percepció d’estrès i ansietat,les expectatives d'autoeficàcia per afrontar els estressors percebuts, les pors i preocupacionsprincipals dels estudiants, així com les seves necessitats de formació específica per afrontar elPràcticum. Els resultats mostren nivells moderats d’ansietat. Les situacions anticipades com amés estressants són l'intent de suïcidi d’un client, l’atac físic, la confidència sobre la comissiód’un delicte, les afirmacions suïcides per part d’un client i la manifestació d‘ira cap a l’estudiant.Les dades també suggereixen que un 44% de la variància de l’ansietat-Estat és pot explicar apartir de l’efecte conjunt de l’ansietat disposicional i les creences disfuncionals, així coml’existència d’una relació negativa entre l’estrès percebut i les expectatives d'autoeficàcia perafrontar-lo. Als estudiants els preocupa no estar a l’alçada de les expectatives, no rebresuficient atenció i orientació dels seus tutors i no saber donar resposta a les demandes delcentre o dels usuaris

Desarrollo de materiales nanocristalinos de base hierro por aleado mecánico

Two alloys, Fe80Nb10B10 and Fe70Ni14Zr6B10, were produced by mechanical alloying. The formation of thenanocrystallites (about 7-8 nm at 80h MA) was detected by X-ray diffraction. After milling for 80 h, differentialscanning calorimetry scans show low-temperature recovery processes and several crystallization processes related with crystal growth and reordering of crystalline phases. The apparent activation energy values are 315 ± 40 kJ mol–1 for alloy A, and 295 ± 20 kJ mol–1 and 320 ± 25 kJ mol–1 for alloy B. Furthermore, a melt-spun Fe-based ribbon was mechanically alloyed to obtain a powdered-like alloy. The increase of the rotation speed and the ball-to-powderweight ratio reduces the necessary time to obtain the powdered form

Basis set effects on the energy and hardness profiles of the hydrogen fluoride dimer

In earlier work, the present authors have shown that hardness profiles are less dependent on the level of calculation than energy profiles for potential energy surfaces (PESs) having pathological behaviors. At variance with energy profiles, hardness profiles always show the correct number of stationary points. This characteristic has been used to indicate the existence of spurious stationary points on the PESs. In the present work, we apply this methodology to the hydrogen fluoride dimer, a classical difficult case for the density functional theory methods

Desenvolupament d'un joc per torns parametritzable amb possibilitat multijugador i I.A.

Els jocs són una de les indústries de software més gran del món de la informàtica. Des dels primers jocs en blanc i negre que simulaven raquetes i una pilota, fins avui en dia, en que el desenvolupament d’un joc porta darrere un equip de professionals tant o més gran que el major dels projectes informàtics del món de les indústries, els jocs han evolucionat més que la majoria de programes. La possibilitat d’elaborar un joc és, a part d’una proposta temptadora (ja que difereix enormement de qualsevol pràctica feta durant la carrera), un repte de caire personal per algú que sempre ha estat en contacte amb videojocs i que, després d’adquirir una sèrie de coneixements indispensables, s’ha proposat d’intentar desenvolupar-ne un des de l’arrel. L’objectiu d’aquest treball és doncs això, aprendre com neix un joc partint de res, i veure totes les complicacions que sorgeixen a l’hora de desenvolupar-lo. Els resultats delt projecte mostren generosament el gran nombre de problemes que sorgeixen en un procés com aquest, però com a conclusions importants cal destacar la satisfacció envers els resultats obtinguts, així com els coneixements que s’han guanyat mitjançant el desenvolupament del programa.

Statistics of transverse mode turn-on dynamics in VCSEL's

The turn-on process of a multimode VCSEL is investigated from a statistical point of view. Special attention is paid to quantities such as time jitter and bit error rate. The single-mode performance of VCSEL¿s during current modulation is compared to that of edge-emitting lasers.

Frequency dynamics of gain-switched injection-locked semiconductor lasers

The frequency dynamics of gain-switched singlemode semiconductor lasers subject to optical injection is investigated. The requirements for low time jitter and reduced frequency chirp operation are studied as a function of the frequency mismatch between the master and slave lasers. Suppression of the power overshoot, typical during gain-switched operation, can be achieved for selected frequency detunings.