Resistance to diet-induced obesity and associated metabolic perturbations in haploinsufficient monocarboxylate transporter 1 mice

The monocarboxylate transporter 1 (MCT1 or SLC16A1) is a carrier of short-chain fatty acids, ketone bodies, and lactate in several tissues. Genetically modified C57BL/6J mice were produced by targeted disruption of the mct1 gene in order to understand the role of this transporter in energy homeostasis. Null mutation was embryonically lethal, but MCT1 (+/-) mice developed normally. However, when fed high fat diet (HFD), MCT1 (+/-) mice displayed resistance to development of diet-induced obesity (24.8% lower body weight after 16 weeks of HFD), as well as less insulin resistance and no hepatic steatosis as compared to littermate MCT1 (+/+) mice used as controls. Body composition analysis revealed that reduced weight gain in MCT1 (+/-) mice was due to decreased fat accumulation (50.0% less after 9 months of HFD) notably in liver and white adipose tissue. This phenotype was associated with reduced food intake under HFD (12.3% less over 10 weeks) and decreased intestinal energy absorption (9.6% higher stool energy content). Indirect calorimetry measurements showed ∼ 15% increase in O2 consumption and CO2 production during the resting phase, without any changes in physical activity. Determination of plasma concentrations for various metabolites and hormones did not reveal significant changes in lactate and ketone bodies levels between the two genotypes, but both insulin and leptin levels, which were elevated in MCT1 (+/+) mice when fed HFD, were reduced in MCT1 (+/-) mice under HFD. Interestingly, the enhancement in expression of several genes involved in lipid metabolism in the liver of MCT1 (+/+) mice under high fat diet was prevented in the liver of MCT1 (+/-) mice under the same diet, thus likely contributing to the observed phenotype. These findings uncover the critical role of MCT1 in the regulation of energy balance when animals are exposed to an obesogenic diet.

Density dependence of the symmetry free energy of hot nuclei

The density and excitation energy dependence of symmetry energy and symmetry free energy for finite nuclei are calculated microscopically in a microcanonical framework, taking into account thermal and expansion effects. A finite-range momentum and density-dependent two-body effective interaction is employed for this purpose. The role of mass, isospin, and equation of state (EOS) on these quantities is also investigated; our calculated results are in consonance with the available experimental data.

Optimization of energy consumption in wastewater pumping

Pumppauksessa arvioidaan olevan niin teknisesti kuin taloudellisestikin huomattavia mahdollisuuksia säästää energiaa. Maailmanlaajuisesti pumppaus kuluttaa lähes 22 % sähkö-moottorien energiantarpeesta. Tietyillä teollisuudenaloilla jopa yli 50 % moottorien käyttämästä sähköenergiasta voi kulua pumppaukseen. Jäteveden pumppauksessa pumppujen toiminta perustuu tyypillisesti on-off käyntiin, jolloin pumpun ollessa päällä se käy täydellä teholla. Monissa tapauksissa pumput ovat myös ylimitoitettuja. Yhdessä nämä seikat johtavat kasvaneeseen energian kulutukseen. Työn teoriaosassa esitellään perusteet jätevesihuollosta ja jäteveden käsittelystä sekä pumppaussysteemin pääkomponentit: pumppu, putkisto, moottori ja taajuusmuuttaja. Työn empiirisessä osassa esitellään työn aikana kehitetty laskuri, jonka avulla voidaan arvioida energiansäästöpotentiaalia jäteveden pumppaussysteemeissä. Laskurilla on mandollista laskea energiansäästöpotentiaali käytettäessä pumpun tuoton ohjaustapana pyörimisnopeuden säätöä taajuusmuuttajalla on-off säädön sijasta. Laskuri ilmoittaa optimaalisimmanpumpun pyörimisnopeuden sekä ominaisenergiankulutuksen. Perustuen laskuriin, kolme kunnallista jätevedenpumppaamoa tutkittiin. Myös laboratorio-testitsuoritettiin laskurin simuloimiseksi sekä energiansäästöpotentiaalin arvioimiseksi. Tutkimukset osoittavat, että jätevedenpumppauksessa on huomattavia mandollisuuksia säästää energiaa pumpun pyörimisnopeutta pienentämällä. Geodeettisen nostokorkeuden ollessa pieni, voidaan energiaa säästää jopa 50 % ja pitkällä aikavälillä säästö voi olla merkittävä. Tulokset vahvistavat myös tarpeen jätevedenpumppaussysteemien toiminnan optimoimiseksi.

A novel approachfor assessing the fatigue strength of ultrasonic impact treated welded structures.

It is commonly observed that complex fabricated structures subject tofatigue loading fail at the welded joints. Some problems can be corrected by proper detail design but fatigue performance can also be improved using post-weld improvement methods. In general, improvement methods can be divided into two main groups: weld geometry modification methods and residual stress modification methods. The former remove weld toe defects and/or reduce the stress concentrationwhile the latter introduce compressive stress fields in the area where fatigue cracks are likely to initiate. Ultrasonic impact treatment (UIT) is a novel post-weld treatment method that influences both the residual stress distribution andimproves the local geometry of the weld. The structural fatigue strength of non-load carrying attachments in the as-welded condition has been experimentally compared to the structural fatigue strength of ultrasonic impact treated welds. Longitudinal attachment specimens made of two thicknesses of steel S355 J0 have been tested for determining the efficiency of ultrasonic impacttreatment. Treated welds were found to have about 50% greater structural fatigue strength, when the slope of the S-N-curve is three. High mean stress fatigue testing based on the Ohta-method decreased the degree of weld improvement only 19%. This indicated that the method could be also applied for large fabricated structures operating under high reactive residual stresses equilibrated within the volume of the structure. The thickness of specimens has no significant effect tothe structural fatigue strength. The fatigue class difference between 5 mm and 8 mm specimen was only 8%. It was hypothesized that the UIT method added a significant crack initiation period to the total fatigue life of the welded joints. Crack initiation life was estimated by a local strain approach. Material parameters were defined using a modified Uniform Material Law developed in Germany. Finite element analysis and X-ray diffraction were used to define, respectively, the stress concentration and mean stress. The theoretical fatigue life was found to have good accuracy comparing to experimental fatigue tests.The predictive behaviour of the local strain approach combined with the uniformmaterial law was excellent for the joint types and conditions studied in this work.

Rockfall susceptibility assessment and remote geological mapping with LiDAR point clouds

Characterizing the geological features and structures in three dimensions over inaccessible rock cliffs is needed to assess natural hazards such as rockfalls and rockslides and also to perform investigations aimed at mapping geological contacts and building stratigraphy and fold models. Indeed, the detailed 3D data, such as LiDAR point clouds, allow to study accurately the hazard processes and the structure of geologic features, in particular in vertical and overhanging rock slopes. Thus, 3D geological models have a great potential of being applied to a wide range of geological investigations both in research and applied geology projects, such as mines, tunnels and reservoirs. Recent development of ground-based remote sensing techniques (LiDAR, photogrammetry and multispectral / hyperspectral images) are revolutionizing the acquisition of morphological and geological information. As a consequence, there is a great potential for improving the modeling of geological bodies as well as failure mechanisms and stability conditions by integrating detailed remote data. During the past ten years several large rockfall events occurred along important transportation corridors where millions of people travel every year (Switzerland: Gotthard motorway and railway; Canada: Sea to sky highway between Vancouver and Whistler). These events show that there is still a lack of knowledge concerning the detection of potential rockfalls, making mountain residential settlements and roads highly risky. It is necessary to understand the main factors that destabilize rocky outcrops even if inventories are lacking and if no clear morphological evidences of rockfall activity are observed. In order to increase the possibilities of forecasting potential future landslides, it is crucial to understand the evolution of rock slope stability. Defining the areas theoretically most prone to rockfalls can be particularly useful to simulate trajectory profiles and to generate hazard maps, which are the basis for land use planning in mountainous regions. The most important questions to address in order to assess rockfall hazard are: Where are the most probable sources for future rockfalls located? What are the frequencies of occurrence of these rockfalls? I characterized the fracturing patterns in the field and with LiDAR point clouds. Afterwards, I developed a model to compute the failure mechanisms on terrestrial point clouds in order to assess the susceptibility to rockfalls at the cliff scale. Similar procedures were already available to evaluate the susceptibility to rockfalls based on aerial digital elevation models. This new model gives the possibility to detect the most susceptible rockfall sources with unprecented detail in the vertical and overhanging areas. The results of the computation of the most probable rockfall source areas in granitic cliffs of Yosemite Valley and Mont-Blanc massif were then compared to the inventoried rockfall events to validate the calculation methods. Yosemite Valley was chosen as a test area because it has a particularly strong rockfall activity (about one rockfall every week) which leads to a high rockfall hazard. The west face of the Dru was also chosen for the relevant rockfall activity and especially because it was affected by some of the largest rockfalls that occurred in the Alps during the last 10 years. Moreover, both areas were suitable because of their huge vertical and overhanging cliffs that are difficult to study with classical methods. Limit equilibrium models have been applied to several case studies to evaluate the effects of different parameters on the stability of rockslope areas. The impact of the degradation of rockbridges on the stability of large compartments in the west face of the Dru was assessed using finite element modeling. In particular I conducted a back-analysis of the large rockfall event of 2005 (265'000 m3) by integrating field observations of joint conditions, characteristics of fracturing pattern and results of geomechanical tests on the intact rock. These analyses improved our understanding of the factors that influence the stability of rock compartments and were used to define the most probable future rockfall volumes at the Dru. Terrestrial laser scanning point clouds were also successfully employed to perform geological mapping in 3D, using the intensity of the backscattered signal. Another technique to obtain vertical geological maps is combining triangulated TLS mesh with 2D geological maps. At El Capitan (Yosemite Valley) we built a georeferenced vertical map of the main plutonio rocks that was used to investigate the reasons for preferential rockwall retreat rate. Additional efforts to characterize the erosion rate were made at Monte Generoso (Ticino, southern Switzerland) where I attempted to improve the estimation of long term erosion by taking into account also the volumes of the unstable rock compartments. Eventually, the following points summarize the main out puts of my research: The new model to compute the failure mechanisms and the rockfall susceptibility with 3D point clouds allows to define accurately the most probable rockfall source areas at the cliff scale. The analysis of the rockbridges at the Dru shows the potential of integrating detailed measurements of the fractures in geomechanical models of rockmass stability. The correction of the LiDAR intensity signal gives the possibility to classify a point cloud according to the rock type and then use this information to model complex geologic structures. The integration of these results, on rockmass fracturing and composition, with existing methods can improve rockfall hazard assessments and enhance the interpretation of the evolution of steep rockslopes. -- La caractérisation de la géologie en 3D pour des parois rocheuses inaccessibles est une étape nécessaire pour évaluer les dangers naturels tels que chutes de blocs et glissements rocheux, mais aussi pour réaliser des modèles stratigraphiques ou de structures plissées. Les modèles géologiques 3D ont un grand potentiel pour être appliqués dans une vaste gamme de travaux géologiques dans le domaine de la recherche, mais aussi dans des projets appliqués comme les mines, les tunnels ou les réservoirs. Les développements récents des outils de télédétection terrestre (LiDAR, photogrammétrie et imagerie multispectrale / hyperspectrale) sont en train de révolutionner l'acquisition d'informations géomorphologiques et géologiques. Par conséquence, il y a un grand potentiel d'amélioration pour la modélisation d'objets géologiques, ainsi que des mécanismes de rupture et des conditions de stabilité, en intégrant des données détaillées acquises à distance. Pour augmenter les possibilités de prévoir les éboulements futurs, il est fondamental de comprendre l'évolution actuelle de la stabilité des parois rocheuses. Définir les zones qui sont théoriquement plus propices aux chutes de blocs peut être très utile pour simuler les trajectoires de propagation des blocs et pour réaliser des cartes de danger, qui constituent la base de l'aménagement du territoire dans les régions de montagne. Les questions plus importantes à résoudre pour estimer le danger de chutes de blocs sont : Où se situent les sources plus probables pour les chutes de blocs et éboulement futurs ? Avec quelle fréquence vont se produire ces événements ? Donc, j'ai caractérisé les réseaux de fractures sur le terrain et avec des nuages de points LiDAR. Ensuite, j'ai développé un modèle pour calculer les mécanismes de rupture directement sur les nuages de points pour pouvoir évaluer la susceptibilité au déclenchement de chutes de blocs à l'échelle de la paroi. Les zones sources de chutes de blocs les plus probables dans les parois granitiques de la vallée de Yosemite et du massif du Mont-Blanc ont été calculées et ensuite comparés aux inventaires des événements pour vérifier les méthodes. Des modèles d'équilibre limite ont été appliqués à plusieurs cas d'études pour évaluer les effets de différents paramètres sur la stabilité des parois. L'impact de la dégradation des ponts rocheux sur la stabilité de grands compartiments de roche dans la paroi ouest du Petit Dru a été évalué en utilisant la modélisation par éléments finis. En particulier j'ai analysé le grand éboulement de 2005 (265'000 m3), qui a emporté l'entier du pilier sud-ouest. Dans le modèle j'ai intégré des observations des conditions des joints, les caractéristiques du réseau de fractures et les résultats de tests géoméchaniques sur la roche intacte. Ces analyses ont amélioré l'estimation des paramètres qui influencent la stabilité des compartiments rocheux et ont servi pour définir des volumes probables pour des éboulements futurs. Les nuages de points obtenus avec le scanner laser terrestre ont été utilisés avec succès aussi pour produire des cartes géologiques en 3D, en utilisant l'intensité du signal réfléchi. Une autre technique pour obtenir des cartes géologiques des zones verticales consiste à combiner un maillage LiDAR avec une carte géologique en 2D. A El Capitan (Yosemite Valley) nous avons pu géoréferencer une carte verticale des principales roches plutoniques que j'ai utilisé ensuite pour étudier les raisons d'une érosion préférentielle de certaines zones de la paroi. D'autres efforts pour quantifier le taux d'érosion ont été effectués au Monte Generoso (Ticino, Suisse) où j'ai essayé d'améliorer l'estimation de l'érosion au long terme en prenant en compte les volumes des compartiments rocheux instables. L'intégration de ces résultats, sur la fracturation et la composition de l'amas rocheux, avec les méthodes existantes permet d'améliorer la prise en compte de l'aléa chute de pierres et éboulements et augmente les possibilités d'interprétation de l'évolution des parois rocheuses.

Non-Linear Journal Bearing Model for Analysis of Superharmonic Vibrations of Rotor Systems

A rotating machine usually consists of a rotor and bearings that supports it. The nonidealities in these components may excite vibration of the rotating system. The uncontrolled vibrations may lead to excessive wearing of the components of the rotating machine or reduce the process quality. Vibrations may be harmful even when amplitudes are seemingly low, as is usually the case in superharmonic vibration that takes place below the first critical speed of the rotating machine. Superharmonic vibration is excited when the rotational velocity of the machine is a fraction of the natural frequency of the system. In such a situation, a part of the machine’s rotational energy is transformed into vibration energy. The amount of vibration energy should be minimised in the design of rotating machines. The superharmonic vibration phenomena can be studied by analysing the coupled rotor-bearing system employing a multibody simulation approach. This research is focused on the modelling of hydrodynamic journal bearings and rotorbearing systems supported by journal bearings. In particular, the non-idealities affecting the rotor-bearing system and their effect on the superharmonic vibration of the rotating system are analysed. A comparison of computationally efficient journal bearing models is carried out in order to validate one model for further development. The selected bearing model is improved in order to take the waviness of the shaft journal into account. The improved model is implemented and analyzed in a multibody simulation code. A rotor-bearing system that consists of a flexible tube roll, two journal bearings and a supporting structure is analysed employing the multibody simulation technique. The modelled non-idealities are the shell thickness variation in the tube roll and the waviness of the shaft journal in the bearing assembly. Both modelled non-idealities may cause subharmonic resonance in the system. In multibody simulation, the coupled effect of the non-idealities can be captured in the analysis. Additionally one non-ideality is presented that does not excite the vibrations itself but affects the response of the rotorbearing system, namely the waviness of the bearing bushing which is the non-rotating part of the bearing system. The modelled system is verified with measurements performed on a test rig. In the measurements the waviness of bearing bushing was not measured and therefore it’s affect on the response was not verified. In conclusion, the selected modelling approach is an appropriate method when analysing the response of the rotor-bearing system. When comparing the simulated results to the measured ones, the overall agreement between the results is concluded to be good.

Etelä-Karjalan energiaselvitys ja maakunnan energiatalouden tulevaisuus

Diplomityössä on selvitetty Etelä-Karjalan maakunnan energian käyttöä nyt ja tulevaisuudessa. Tavoitteena on selvittää eri energialähteiden hankintavaihtoehtoja, sekä eri energialähteiden käytön kehittymissuunnat seuraavan 10 - 20 vuoden kuluessa. Diplomityö on tehty Etelä-Karjalan liiton toimeksiannosta ja sitä tullaan käyttämään taustaselvityksenä maakuntakaavan laadinnassa sekä maakunnan aluevarauksia määriteltäessä. Tarkoituksena on arvioida miten energiahuollon rakenne tulee muuttumaan tulevaisuudessa ja mikä merkitys tulevaisuuden energiaratkaisuilla on alueiden käyttöön ja aluerakenteeseen liittyen. Etelä-Karjala on osa Euroopan suurinta metsäteollisuuskeskittymää ja maakunta on Suomen suurimpia teollisuuden energian- ja sähkönkäyttäjiä. Etelä-Karjalan vahva metsäteollisuus ja sen käyttämät puupolttoaineet sekä sijainti Venäjän maakaasuvarojen läheisyydessä ja kattava maakaasuverkko vaikuttavat merkittävästi maakunnan energiataseeseen. Vuonna 2007 Etelä-Karjalan primäärienergiankäyttö oli 24,3 TWh, tästä uusiutuvien energialähteiden osuus oli 68 % ja fossiilisten energialähteiden osuus 22 %. Etelä-Karjalan energiatalouden tulevaisuuteen vaikuttaa merkittävästi maakunnan metsäteollisuuden tulevaisuus. Tiukentuvan energia- ja ilmastopolitiikan ja ympäristömääräysten myötä maakunnan energiatehokkuutta on parannettava kaikilla sektoreilla. Maakunnan energiankulutusta voidaan vähentää tehostamalla energiantuotantoa, tiivistämällä yhdyskuntarakennetta ja lisäämällä bioenergian käyttöä energiantuotannossa. Etelä-Karjalassa on myös potentiaalia lisätä vaihtoehtoisten energialähteiden osuutta maakunnan energiatalouden tulevaisuudessa.

Advances in modelling of mechatronic systems: the toolset FASIM_C++ for the simulation of vehicle dynamics

The increasing complexity of controller systems, applied in modern passenger cars, requires adequate simulation tools. The toolset FASIM_C++, described in the following, uses complex vehicle models in three-dimensional vehicle dynamics simulation. The structure of the implemented dynamic models and the generation of the equations of motion applying the method of kinematic differentials is explained briefly. After a short introduction in methods of event handling, several vehicle models and applications like controller development, roll-over simulation and real-time-simulation are explained. Finally some simulation results are presented.

The band structure of Cd0

The Augmented Pl ane Wave Method has been used to calculate the one-electron energy band structure of CdO. Energy eigenva l ues were calculated along three symmetry lines and for some other general wave-vectors of interest.

Synthesis of Bio-Compatible SPION–based Aqueous Ferrofluids and Evaluation of RadioFrequency Power Loss for Magnetic Hyperthermia

Bio-compatible magnetic fluids having high saturation magnetization find immense applications in various biomedical fields. Aqueous ferrofluids of superparamagnetic iron oxide nanoparticles with narrow size distribution, high shelf life and good stability is realized by controlled chemical co-precipitation process. The crystal structure is verified by X-ray diffraction technique. Particle sizes are evaluated by employing Transmission electron microscopy. Room temperature and low-temperature magnetic measurements were carried out with Superconducting Quantum Interference Device. The fluid exhibits good magnetic response even at very high dilution (6.28 mg/cc). This is an advantage for biomedical applications, since only a small amount of iron is to be metabolised by body organs. Magnetic field induced transmission measurements carried out at photon energy of diode laser (670 nm) exhibited excellent linear dichroism. Based on the structural and magnetic measurements, the power loss for the magnetic nanoparticles under study is evaluated over a range of radiofrequencies.

Verbesserung der seismischen Kapazität von Mauerwerkswänden durch Verwendung von Elastomerlagern

Ein großer Teil der Schäden wie auch der Verluste an Gesundheit und Leben im Erdbebenfall hat mit dem frühzeitigen Versagen von Mauerwerksbauten zu tun. Unbewehrtes Mauerwerk, wie es in vielen Ländern üblich ist, weist naturgemäß einen begrenzten Erdbebenwiderstand auf, da Zugspannungen und Zugkräfte nicht wie bei Stahlbeton- oder Stahlbauten aufgenommen werden können. Aus diesem Grund wurde bereits mit verschiedenen Methoden versucht, die Tragfähigkeit von Mauerwerk im Erdbebenfall zu verbessern. Modernes Mauerwerk kann auch als bewehrtes oder eingefasstes Mauerwerk hergestellt werden. Bei bewehrtem Mauerwerk kann durch die Bewehrung der Widerstand bei Beanspruchung als Scheibe wie als Platte verbessert werden, während durch Einfassung mit Stahlbetonelementen in erster Linie die Scheibentragfähigkeit sowie die Verbindung zu angrenzenden Bauteilen verbessert wird. Eine andere interessante Möglichkeit ist das Aufbringen textiler Mauerwerksverstärkungen oder von hochfesten Lamellen. In dieser Arbeit wird ein ganz anderer Weg beschritten, indem weiche Fugen Spannungsspitzen reduzieren sowie eine höhere Verformbarkeit gewährleiten. Dies ist im Erdbebenfall sehr hilfreich, da die Widerstandfähigkeit eines Bauwerks oder Bauteils letztlich von der Energieaufnahmefähigkeit, also dem Produkt aus Tragfähigkeit und Verformbarkeit bestimmt wird. Wenn also gleichzeitig durch die weichen Fugen keine Schwächung oder sogar eine Tragfähigkeitserhöhung stattfindet, kann der Erdbebenwiderstand gesteigert werden. Im Kern der Dissertation steht die Entwicklung der Baukonstruktion einer Mauerwerkstruktur mit einer neuartigen Ausbildung der Mauerwerksfugen, nämlich Elastomerlager und Epoxydharzkleber anstatt üblichem Dünnbettmörtel. Das Elastomerlager wird zwischen die Steinschichten einer Mauerwerkswand eingefügt und damit verklebt. Die Auswirkung dieses Ansatzes auf das Verhalten der Mauerwerkstruktur wird unter dynamischer und quasi-statischer Last numerisch und experimentell untersucht und dargestellt.

Effect of Auger recombination and leakage on the droop in InGaN/GaN quantum well LEDs

We investigate the effect of the epitaxial structure and the acceptor doping profile on the efficiency droop in InGaN/GaN LEDs by the physics based simulation of experimental internal quantum efficiency (IQE) characteristics. The device geometry is an integral part of our simulation approach. We demonstrate that even for single quantum well LEDs the droop depends critically on the acceptor doping profile. The Auger recombination was found to increase stronger than with the third power of the carrier density and has been found to dominate the droop in the roll over zone of the IQE. The fitted Auger coefficients are in the range of the values predicted by atomistic simulations.

Simulation of interlaminar and intralaminar damage in polymer-based composites for aeronautical applications under impact loading

La aplicación de materiales compuestos de matriz polimérica reforzados mediante fibras largas (FRP, Fiber Reinforced Plastic), está en gradual crecimiento debido a las buenas propiedades específicas y a la flexibilidad en el diseño. Uno de los mayores consumidores es la industria aeroespacial, dado que la aplicación de estos materiales tiene claros beneficios económicos y medioambientales. Cuando los materiales compuestos se aplican en componentes estructurales, se inicia un programa de diseño donde se combinan ensayos reales y técnicas de análisis. El desarrollo de herramientas de análisis fiables que permiten comprender el comportamiento mecánico de la estructura, así como reemplazar muchos, pero no todos, los ensayos reales, es de claro interés. Susceptibilidad al daño debido a cargas de impacto fuera del plano es uno de los aspectos de más importancia que se tienen en cuenta durante el proceso de diseño de estructuras de material compuesto. La falta de conocimiento de los efectos del impacto en estas estructuras es un factor que limita el uso de estos materiales. Por lo tanto, el desarrollo de modelos de ensayo virtual mecánico para analizar la resistencia a impacto de una estructura es de gran interés, pero aún más, la predicción de la resistencia residual después del impacto. En este sentido, el presente trabajo abarca un amplio rango de análisis de eventos de impacto a baja velocidad en placas laminadas de material compuesto, monolíticas, planas, rectangulares, y con secuencias de apilamiento convencionales. Teniendo en cuenta que el principal objetivo del presente trabajo es la predicción de la resistencia residual a compresión, diferentes tareas se llevan a cabo para favorecer el adecuado análisis del problema. Los temas que se desarrollan son: la descripción analítica del impacto, el diseño y la realización de un plan de ensayos experimentales, la formulación e implementación de modelos constitutivos para la descripción del comportamiento del material, y el desarrollo de ensayos virtuales basados en modelos de elementos finitos en los que se usan los modelos constitutivos implementados.

A potential energy surface for the ground state of formaldehyde, H2CO(1A1)

A model potential energy function for the ground state of H2CO has been derived which covers the whole space of the six internal coordinates. This potential reproduces the experimental energy, geometry and quadratic force field of formaldehyde, and dissociates correctly to all possible atom, diatom and triatom fragments. Thus there are good reasons for believing it to be close to the true potential energy surface except in regions where both hydrogen atoms are close to the oxygen. It leads to the prediction that there should be a metastable singlet hydroxycarbene HCOH which has a planar trans structure and an energy of 2•31 eV above that of equilibrium formaldehyde. The reaction path for dissociation into H2 + CO is predicted to pass through a low symmetry transition state with an activation energy of 4•8 eV. Both of these predictions are in good agreement with recently published ab initio calculations.

Electronic transitions and bonding properties in a series of five-coordinate “16-electron” complexes [Mn(CO)3(L2)]− (L2=chelating redox-active π-donor ligand)

In this article we present for the first time accurate density functional theory (DFT) and time-dependent (TD) DFT data for a series of electronically unsaturated five-coordinate complexes [Mn(CO)(3)(L-2)](-), where L-2 stands for a chelating strong pi-donor ligand represented by catecholate, dithiolate, amidothiolate, reduced alpha-diimine (1,4-dialkyl-1,4-diazabutadiene (R-DAB), 2,2'-bipyridine) and reduced 2,2'-biphosphinine types. The single-crystal X-ray structure of the unusual compound [Na(BPY)][Mn(CO)(3)(BPY)]center dot Et2O and the electronic absorption spectrum of the anion [Mn(CO)(3)(BPY)](-) are new in the literature. The nature of the bidentate ligand determines the bonding in the complexes, which varies between two limiting forms: from completely pi-delocalized diamagnetic {(CO)(3)Mn-L-2}(-) for L-2 = alpha-diimine or biphosphinine, to largely valence-trapped {(CO)(3)Mn-1-L-2(2-)}(-) for L-2(2-) = catecholate, where the formal oxidation states of Mn and L-2 can be assigned. The variable degree of the pi-delocalization in the Mn(L-2) chelate ring is indicated by experimental resonance Raman spectra of [Mn(CO)(3)(L-2)](-) (L-2=3,5-di-tBu-catecholate and iPr-DAB), where accurate assignments of the diagnostically important Raman bands have been aided by vibrational analysis. The L-2 = catecholate type of complexes is known to react with Lewis bases (CO substitution, formation of six-coordinate adducts) while the strongly pi-delocalized complexes are inert. The five-coordinate complexes adopt usually a distorted square pyramidal geometry in the solid state, even though transitions to a trigonal bipyramid are also not rare. The experimental structural data and the corresponding DFT-computed values of bond lengths and angles are in a very good agreement. TD-DFT calculations of electronic absorption spectra of the studied Mn complexes and the strongly pi-delocalized reference compound [Fe(CO)(3)(Me-DAB)] have reproduced qualitatively well the experimental spectra. Analyses of the computed electronic transitions in the visible spectroscopic region show that the lowest-energy absorption band always contains a dominant (in some cases almost exclusive) contribution from a pi(HOMO) -> pi*(LUMO) transition within the MnL2 metallacycle. The character of this optical excitation depends strongly on the composition of the frontier orbitals, varying from a partial L-2 -> Mn charge transfer (LMCT) through a fully delocalized pi(MnL2) -> pi*(MnL2) situation to a mixed (CO)Mn -> L-2 charge transfer (LLCT/MLCT). The latter character is most apparent in the case of the reference complex [Fe(CO)(3)(Me-DAB)]. The higher-lying, usually strongly mixed electronic transitions in the visible absorption region originate in the three lower-lying occupied orbitals, HOMO - 1 to HOMO - 3, with significant metal-d contributions. Assignment of these optical excitations to electronic transitions of a specific type is difficult. A partial LLCT/MLCT character is encountered most frequently. The electronic absorption spectra become more complex when the chelating ligand L-2, such as 2,2'-bipyridine, features two or more closely spaced low-lying empty pi* orbitals.