Theoretical study of the second-order vibrational Stark effect

The behaviour of the harmonic infrared frequency of diatomic molecules subjected to moderate static uniform electric fields is analysed. The potential energy expression has been developed as a function of a static uniform electric field, which brings about a formulation describing the frequency versus field strength curve. With the help of the first and second derivatives of the expressions obtained, which correspond to the first- and second-order Stark effects, it was possible to find the maxima of the frequency versus field strength curves for a series of molecules using a Newton-Raphson search. A method is proposed which requires only the calculation of a few energy derivatives at a particular value of the field strength. At the same time, the expression for the dependence of the interatomic distance on the electric field strength is derived and the minimum of this curve is found for the same species. Derived expressions and numerical results are discussed and compared with other studi

The curvature of the conical intersection seam: an approximate second-order analysis

We present a method for analyzing the curvature (second derivatives) of the conical intersection hyperline at an optimized critical point. Our method uses the projected Hessians of the degenerate states after elimination of the two branching space coordinates, and is equivalent to a frequency calculation on a single Born-Oppenheimer potential-energy surface. Based on the projected Hessians, we develop an equation for the energy as a function of a set of curvilinear coordinates where the degeneracy is preserved to second order (i.e., the conical intersection hyperline). The curvature of the potential-energy surface in these coordinates is the curvature of the conical intersection hyperline itself, and thus determines whether one has a minimum or saddle point on the hyperline. The equation used to classify optimized conical intersection points depends in a simple way on the first- and second-order degeneracy splittings calculated at these points. As an example, for fulvene, we show that the two optimized conical intersection points of C2v symmetry are saddle points on the intersection hyperline. Accordingly, there are further intersection points of lower energy, and one of C2 symmetry - presented here for the first time - is found to be the global minimum in the intersection space

The curvature of the conical intersection seam: an approximate second-order analysis

We present a method for analyzing the curvature (second derivatives) of the conical intersection hyperline at an optimized critical point. Our method uses the projected Hessians of the degenerate states after elimination of the two branching space coordinates, and is equivalent to a frequency calculation on a single Born-Oppenheimer potential-energy surface. Based on the projected Hessians, we develop an equation for the energy as a function of a set of curvilinear coordinates where the degeneracy is preserved to second order (i.e., the conical intersection hyperline). The curvature of the potential-energy surface in these coordinates is the curvature of the conical intersection hyperline itself, and thus determines whether one has a minimum or saddle point on the hyperline. The equation used to classify optimized conical intersection points depends in a simple way on the first- and second-order degeneracy splittings calculated at these points. As an example, for fulvene, we show that the two optimized conical intersection points of C2v symmetry are saddle points on the intersection hyperline. Accordingly, there are further intersection points of lower energy, and one of C2 symmetry - presented here for the first time - is found to be the global minimum in the intersection space

Metal binding selectivity of oxa-aza macrocyclic ligand: a DFT study of first- and second-row transition metal for four coordination systems

A detailed theoretical study of the 1,7,1l,17-tetraoxa-2,6,12,16-tetraaza-cycloeicosane ligand ([20]AneN(4)O(4)) coordinated to Fe2+, Co2+, Ni2+, Ru2+, Rh2+, and Pd2+ transition metal ions was carried out with the B3LYP method. Two different cases were performed: when nitrogen is the donor atom (1a (q) ) and also with the oxygen as the donor atom (1b (q) ). For all the cases performed in this study 1a (q) structures were always more stable than the 1b (q) ones. Considering each row is possible to see that the energy increases with the increase of the atomic number. The M2+ cation binding energies for the 1a (q) complexes increase with the following order: Fe2+ < Ru2+ < Co2+ < Ni2+ < Rh2+ < Pd2+.

First- and second-row transition metal oxa-aza macrocyclic complexes: a DFT study of an octahedral conformation

A theoretical study of structures of the 1,7,1 l,17-tetraoxa-2,6,12,16-tetraaza-cycloeicosane ligand ([20]AneN(4)O(4)) coordinated to Fe2+, Co2+, Ni2+, Ru2+, Rh2+, and Pd2+ transition metals ions was carried out with the DFT/B3LYP method. Complexes were fully optimized in C-s symmetry with the metal ions coordinated either to nitrogen (1a) or oxygen atoms (1b). For all the cases performed in this work, 1a was always more stable than 1b. Considering each row it is possible to see that the binding energy increases with the atomic number. The M2+ cation binding energies increase in the following order: Fe2+ < Ru2+ < Co2+ < Ni2+ < Rh2+ < Pd2+. In addition, it was observed the preference of Pd2+ and Rh2+ complexes for a tetrahedral arrangement, while Fe2+, Ru2+, Co2+, Ni2+ complexes had a preference for the octahedral arrangement. From the orbital representation results, it was seen that 1b unsymmetrical orbitals may influence the susceptibility over metal ions orientation toward heteroatoms orbitals.

Methodological approach to the first and second lactate threshold in incremental cardiopulmonary exercise testing

Determination of an 'anaerobic threshold' plays an important role in the appreciation of an incremental cardiopulmonary exercise test and describes prominent changes of blood lactate accumulation with increasing workload. Two lactate thresholds are discerned during cardiopulmonary exercise testing and used for physical fitness estimation or training prescription. A multitude of different terms are, however, found in the literature describing the two thresholds. Furthermore, the term 'anaerobic threshold' is synonymously used for both, the 'first' and the 'second' lactate threshold, bearing a great potential of confusion. The aim of this review is therefore to order terms, present threshold concepts, and describe methods for lactate threshold determination using a three-phase model with reference to the historical and physiological background to facilitate the practical application of the term 'anaerobic threshold'.

Selected topics in the Hydrodynamics of floating offshore wind turbines: heave damping and second order surge motions

La Energía eléctrica producida mediante tecnología eólica flotante es uno de los recursos más prometedores para reducir la dependencia de energía proveniente de combustibles fósiles. Esta tecnología es de especial interés en países como España, donde la plataforma continental es estrecha y existen pocas áreas para el desarrollo de estructuras fijas. Entre los diferentes conceptos flotantes, esta tesis se ha ocupado de la tipología semisumergible. Estas plataformas pueden experimentar movimientos resonantes en largada y arfada. En largada, dado que el periodo de resonancia es largo estos puede ser inducidos por efectos de segundo orden de deriva lenta que pueden tener una influencia muy significativa en las cargas en los fondeos. En arfada las fuerzas de primer orden pueden inducir grandes movimientos y por tanto la correcta determinación del amortiguamiento es esencial para la analizar la operatividad de la plataforma. Esta tesis ha investigado estos dos efectos, para ello se ha usado como caso base el diseño de una plataforma desarrollada en el proyecto Europeo Hiprwind. La plataforma se compone de 3 columnas cilíndricas unidas mediante montantes estructurales horizontales y diagonales, Los cilindros proporcionan flotabilidad y momentos adrizante. A la base de cada columna se le ha añadido un gran “Heave Plate” o placa de cierre. El diseño es similar a otros diseños previos (Windfloat). Se ha fabricado un modelo a escala de una de las columnas para el estudio detallado del amortiguamiento mediante oscilaciones forzadas. Las dimensiones del modelo (1m diámetro en la placa de cierre) lo hacen, de los conocidos por el candidato, el mayor para el que se han publicado datos. El diseño del cilindro se ha realizado de tal manera que permite la fijación de placas de cierre planas o con refuerzo, ambos modelos se han fabricado y analizado. El modelo con refuerzos es una reproducción exacta del diseño a escala real incluyendo detalles distintivos del mismo, siendo el más importante la placa vertical perimetral. Los ensayos de oscilaciones forzadas se han realizado para un rango de frecuencias, tanto para el disco plano como el reforzado. Se han medido las fuerzas durante los ensayos y se han calculado los coeficientes de amortiguamiento y de masa añadida. Estos coeficientes son necesarios para el cálculo del fondeo mediante simulaciones en el dominio del tiempo. Los coeficientes calculados se han comparado con la literatura existente, con cálculos potenciales y por ultimo con cálculos CFD. Para disponer de información relevante para el diseño estructural de la plataforma se han medido y analizado experimentalmente las presiones en la parte superior e inferior de cada placa de cierre. Para la correcta estimación numérica de las fuerzas de deriva lenta en la plataforma se ha realizado una campaña experimental que incluye ensayos con modelo cautivo de la plataforma completa en olas bicromaticas. Pese a que estos experimentos no reproducen un escenario de oleaje realista, los mismos permiten una verificación del modelo numérico mediante la comparación de fuerzas medidas en el modelo físico y el numérico. Como resultados de esta tesis podemos enumerar las siguientes conclusiones. 1. El amortiguamiento y la masa añadida muestran una pequeña dependencia con la frecuencia pero una gran dependencia con la amplitud del movimiento. siendo coherente con investigaciones existentes. 2. Las medidas con la placa de cierre reforzada con cierre vertical en el borde, muestra un amortiguamiento significativamente menor comparada con la placa plana. Esto implica que para ensayos de canal es necesario incluir estos detalles en el modelo. 3. La masa añadida no muestra grandes variaciones comparando placa plana y placa con refuerzos. 4. Un coeficiente de amortiguamiento del 6% del crítico se puede considerar conservador para el cálculo en el dominio de la frecuencia. Este amortiguamiento es equivalente a un coeficiente de “drag” de 4 en elementos de Morison cuadráticos en las placas de cierre usadas en simulaciones en el dominio del tiempo. 5. Se han encontrado discrepancias en algunos valores de masa añadida y amortiguamiento de la placa plana al comparar con datos publicados. Se han propuesto algunas explicaciones basadas en las diferencias en la relación de espesores, en la distancia a la superficie libre y también relacionadas con efectos de escala. 6. La presión en la placa con refuerzos son similares a las de la placa plana, excepto en la zona del borde donde la placa con refuerzo vertical induce una gran diferencias de presiones entre la cara superior e inferior. 7. La máxima diferencia de presión escala coherentemente con la fuerza equivalente a la aceleración de la masa añadida distribuida sobre la placa. 8. Las masas añadidas calculadas con el código potencial (WADAM) no son suficientemente precisas, Este software no contempla el modelado de placas de pequeño espesor con dipolos, la poca precisión de los resultados aumenta la importancia de este tipo de elementos al realizar simulaciones con códigos potenciales para este tipo de plataformas que incluyen elementos de poco espesor. 9. Respecto al código CFD (Ansys CFX) la precisión de los cálculos es razonable para la placa plana, esta precisión disminuye para la placa con refuerzo vertical en el borde, como era de esperar dado la mayor complejidad del flujo. 10. Respecto al segundo orden, los resultados, en general, muestran que, aunque la tendencia en las fuerzas de segundo orden se captura bien con los códigos numéricos, se observan algunas reducciones en comparación con los datos experimentales. Las diferencias entre simulaciones y datos experimentales son mayores al usar la aproximación de Newman, que usa únicamente resultados de primer orden para el cálculo de las fuerzas de deriva media. 11. Es importante remarcar que las tendencias observadas en los resultados con modelo fijo cambiarn cuando el modelo este libre, el impacto que los errores en las estimaciones de fuerzas segundo orden tienen en el sistema de fondeo dependen de las condiciones ambientales que imponen las cargas ultimas en dichas líneas. En cualquier caso los resultados que se han obtenido en esta investigación confirman que es necesaria y deseable una detallada investigación de los métodos usados en la estimación de las fuerzas no lineales en las turbinas flotantes para que pueda servir de guía en futuros diseños de estos sistemas. Finalmente, el candidato espera que esta investigación pueda beneficiar a la industria eólica offshore en mejorar el diseño hidrodinámico del concepto semisumergible. ABSTRACT Electrical power obtained from floating offshore wind turbines is one of the promising resources which can reduce the fossil fuel energy consumption and cover worldwide energy demands. The concept is the most competitive in countries, such as Spain, where the continental shelf is narrow and does not provide space for fixed structures. Among the different floating structures concepts, this thesis has dealt with the semisubmersible one. Platforms of this kind may experience resonant motions both in surge and heave directions. In surge, since the platform natural period is long, such resonance can be excited with second order slow drift forces and may have substantial influence on mooring loads. In heave, first order forces can induce significant motion, whose damping is a crucial factor for the platform downtime. These two topics have been investigated in this thesis. To this aim, a design developed during HiPRWind EU project, has been selected as reference case study. The platform is composed of three cylindrical legs, linked together by a set of structural braces. The cylinders provide buoyancy and restoring forces and moments. Large circular heave plates have been attached to their bases. The design is similar to other documented in literature (e.g. Windfloat), which implies outcomes could have a general value. A large scale model of one of the legs has been built in order to study heave damping through forced oscillations. The final dimensions of the specimen (one meter diameter discs) make it, to the candidate’s knowledge, the largest for which data has been published. The model design allows for the fitting of either a plain solid heave plate or a flapped reinforced one; both have been built. The latter is a model scale reproduction of the prototype heave plate and includes some distinctive features, the most important being the inclusion of a vertical flap on its perimeter. The forced oscillation tests have been conducted for a range of frequencies and amplitudes, with both the solid plain model and the vertical flap one. Forces have been measured, from which added mass and damping coefficients have been obtained. These are necessary to accurately compute time-domain simulations of mooring design. The coefficients have been compared with literature, and potential flow and CFD predictions. In order to provide information for the structural design of the platform, pressure measurements on the top and bottom side of the heave discs have been recorded and pressure differences analyzed. In addition, in order to conduct a detailed investigation on the numerical estimations of the slow-drift forces of the HiPRWind platform, an experimental campaign involving captive (fixed) model tests of a model of the whole platform in bichromatic waves has been carried out. Although not reproducing the more realistic scenario, these tests allowed a preliminary verification of the numerical model based directly on the forces measured on the structure. The following outcomes can be enumerated: 1. Damping and added mass coefficients show, on one hand, a small dependence with frequency and, on the other hand, a large dependence with the motion amplitude, which is coherent with previously published research. 2. Measurements with the prototype plate, equipped with the vertical flap, show that damping drops significantly when comparing this to the plain one. This implies that, for tank tests of the whole floater and turbine, the prototype plate, equipped with the flap, should be incorporated to the model. 3. Added mass values do not suffer large alterations when comparing the plain plate and the one equipped with a vertical flap. 4. A conservative damping coefficient equal to 6% of the critical damping can be considered adequate for the prototype heave plate for frequency domain analysis. A corresponding drag coefficient equal to 4.0 can be used in time domain simulations to define Morison elements. 5. When comparing to published data, some discrepancies in added mass and damping coefficients for the solid plain plate have been found. Explanations have been suggested, focusing mainly on differences in thickness ratio and distance to the free surface, and eventual scale effects. 6. Pressures on the plate equipped with the vertical flap are similar in magnitude to those of the plain plate, even though substantial differences are present close to the edge, where the flap induces a larger pressure difference in the reinforced case. 7. The maximum pressure difference scales coherently with the force equivalent to the acceleration of the added mass, distributed over the disc surface. 8. Added mass coefficient values predicted with the potential solver (WADAM) are not accurate enough. The used solver does not contemplate modeling thin plates with doublets. The relatively low accuracy of the results highlights the importance of these elements when performing potential flow simulations of offshore platforms which include thin plates. 9. For the full CFD solver (Ansys CFX), the accuracy of the computations is found reasonable for the plain plate. Such accuracy diminishes for the disc equipped with a vertical flap, an expected result considering the greater complexity of the flow. 10. In regards to second order effects, in general, the results showed that, although the main trend in the behavior of the second-order forces is well captured by the numerical predictions, some under prediction of the experimental values is visible. The gap between experimental and numerical results is more pronounced when Newman’s approximation is considered, making use exclusively of the mean drift forces calculated in the first-order solution. 11. It should be observed that the trends observed in the fixed model test may change when the body is free to float, and the impact that eventual errors in the estimation of the second-order forces may have on the mooring system depends on the characteristics of the sea conditions that will ultimately impose the maximum loads on the mooring lines. Nevertheless, the preliminary results obtained in this research do confirm that a more detailed investigation of the methods adopted for the estimation of the nonlinear wave forces on the FOWT would be welcome and may provide some further guidance for the design of such systems. As a final remark, the candidate hopes this research can benefit the offshore wind industry in improving the hydrodynamic design of the semi-submersible concept.

Transmission comparison of ultra-long Raman fibre laser based amplification with first and dual order Raman amplification using 10×118 Gbit/s DP-QPSK

Experimental investigations of 10×118 Gbit/s DP-QPSK WDM transmission using three types of distributed Raman amplification techniques are presented. Novel ultra-long Raman fibre laser based amplification with second order counter-propagated pumping is compared with conventional first order and dual order counter-pumped Raman amplification. We demonstrate that URFL based amplification can extend the transmission reach up to a distance of 7520 km in comparison with 5010 km and 6180 km using first order and dual order Raman amplification respectively. © 2014 IEEE.

Folding, calcium binding, and structural characterization of a concatemer of the first and second ligand-binding modules of the low-density lipoprotein receptor

The ligand-binding domain of the low-density lipoprotein (LDL) receptor is comprised of seven tandemly repeated ligand-binding modules, each being approximately 40 amino acids long and containing six conserved cysteine residues. We have expressed and characterized a concatemer of the first two modules (LB1 and LB2) of the human LDL receptor. Oxidative folding of the recombinant concatemer (rLB(1-2)), in the presence of calcium ions, gave a single dominant isomer with six disulfide bonds. Peptic cleavage of the short Linker region that connects the last cysteine residue of LB1 and the first cysteine residue of LB2 yielded two discrete fragments, thus excluding the presence of intermodule disulfide bonds. The N-terminal module, LB1, reacted with a conformation-specific monoclonal antibody (IgG-C7) made to LB1 in the native LDL receptor. From this, we concluded that the first module was correctly folded, with the same set of disulfide bonds as LB1 of the LDL receptor. The disulfide bond connections of LB2 were identified from mass spectral analysis of fragments formed by digestion of the C-terminal peptic fragment with elastase. These data showed that the disulfide bonds of LB2 connected Cys(I) and Cys(III), Cys(II) and Cys(V), and Cys(IV) and Cys(VI). This pattern is identical to that found for recombinant LB1 and LB2. The concatemer has two high-affinity calcium-binding sites, one per module. An analysis of the secondary chemical shifts of C alpha protons shows that the conformations of LB1 and LB2 in the concatemer are very similar to those of the individual modules, with no evidence for strong interactions between the two modules.

Basis set convergence in Hartree-Fock calculations of some diatomic molecules containing first and second-row atoms

Investiga-se a convergência de conjuntos de bases em direção ao limite numérico da energia Hartree-Fock (HF) total para as seqüências hierárquicas dos conjuntos de bases XZP e ccpVXZ. Para as duas hierarquias, melhoramentos significativos são obtidos com cada incremento em X. Para estimar o limite do conjunto de base completo, uma forma exponencial foi usada. Entre as várias aproximações consideradas aqui, uma extrapolação exponencial de três parâmetros aplicada aos resultados TZP, QZP e 5ZP deu os limites do conjunto de bases mais precisos. Em adição, energias HF dos orbitais moleculares ocupados mais altos de algumas moléculas diatômicas foram calculadas com o conjunto 5ZP e comparadas com as correspondentes obtidas com o conjunto cc-pV5Z e com um método numérico HF.

First- and second-time parents’ couple relationship: from pregnancy to second year postpartum

First- and second-time parents’ couple relationships were studied from early pregnancy to the second year postpartum. The Relationship Questionnaire (RQ) was administered to Portuguese couples (N = 82), first- or second-time parents, at the first, second and third pregnancy trimester, childbirth, 3 and 18 months postpartum. Adverse changes in positive and negative partner relationship dimensions were reported from early pregnancy to the second year postpartum by all participants; in the same way by mothers and fathers and by first- and second-time parents. Second-time parents reported a worse couple relationship (lower RQ-positive scores) than first-time parents, but only during pregnancy. Results from the present study suggest a decline in partner relationship quality during the transition to parenthood both in mothers and fathers, as well as in first- and second-time parents.

First-and second-best allocations under economic and environmental uncertainty

This paper uses a micro-founded DSGE model to compare second-best optimal environmental policy and the resulting allocation to first-best allocation. The focus is on the source and size of uncertainty, and how this affects optimal choices and the inferiority of second best vis-à-vis first best.

Analysis of the first and second internal transcribed spacer sequences of the ribosomal DNA in Biomphalaria tenagophila complex (Mollusca: Planorbidae)

The first and second internal transcribed spacer regions (ITS1 and ITS2) of the ribosomal DNA of Biomphalaria tenagophila complex (B. tenagophila, B. occidentalis, and B. t. guaibensis) were sequenced and compared. The alignment lengths of these regions were about 655 bp and 481 bp, respectively. Phylogenetic relationships among the Biomphalaria species were inferred by Maximum Parsimony and Neighbor-joining methods. The phylogenetic trees produced, in most of the cases, were in accordance with morphological systematics and other molecular data previously obtained by polymerase chain reaction and restriction fragment length polymorphism analysis. The present results provide support for the proposal that B. tenagophila represents a complex comprising B. tenagophila, B. occidentalis and B. t. guaibensis.

A population-based study of first and second-line drug-resistant tuberculosis in a high-burden area of the Mexico/United States border

The resistance of 139 Mycobacterium tuberculosis (MTB) isolates from the city of Monterrey, Northeast Mexico, to first and second-line anti-TB drugs was analysed. A total of 73 isolates were susceptible and 66 were resistant to anti-TB drugs. Monoresistance to streptomycin, isoniazid (INH) and ethambutol was observed in 29 cases. Resistance to INH was found in 52 cases and in 29 cases INH resistance was combined with resistance to two or three drugs. A total of 24 isolates were multidrug-resistant (MDR) resistant to at least INH and rifampicin and 11 MDR cases were resistant to five drugs. The proportion of MDR-TB among new TB cases in our target population was 0.72% (1/139 cases). The proportion of MDR-TB among previously treated cases was 25.18% (35/139 cases). The 13 polyresistant and 24 MDR isolates were assayed against the following seven second-line drugs: amikacin (AMK), kanamycin (KAN), capreomycin (CAP), clofazimine (CLF), ethionamide (ETH), ofloxacin (OFL) and cycloserine (CLS). Resistance to CLF, OFL or CLS was not observed. Resistance was detected to ETH (10.80%) and to AMK (2.70%), KAN (2.70%) and CAP (2.70%). One isolate of MDR with primary resistance was also resistant to three second-line drugs. Monterrey has a high prevalence of MDR-TB among previously treated cases and extensively drug-resistant-MTB strains may soon appear.

Cultural self-identification(s) and personal social networks among first and second-generation immigrants

L’estudi examina les relacions entre (1) les xarxes socials personals de la població immigrant resident a Barcelona i (2) les seves identitats culturals múltiples. L’objectiu principal de l’estudi és entendre com el contingut i l’estructura de les relacions socials dels immigrants facilita o dificulta (1) tenir un sentiment de pertinença a les noves cultures d’acollida, la catalana i la espanyola, i (2) la integració d’aquestes noves identitats socioculturals amb la seva identitat d’origen en una nova identitat bicultural cohesiva. El nostre plantejament inicial era que els immigrants amb xarxes socials més diverses des del punt de vista de la seva composició cultural tindrien més recursos socials i experiències cognitives més diverses , factors que afavoreixen les identificacions múltiples i la participació cívica. Els resultats de l’estudi mostren que el grau d’identificació dels participants amb la seva cultura ètnica o d’origen és força alt i, en certa mesura, més alt en comparació amb les cultures d’acollida ( catalana, cívica i espanyola). Tanmateix, el vincle dels participants amb les cultures d’acollida (p. ex., la cultura catalana) és prou rellevant per a indicar una orientació bicultural (catalana i ètnica). Les anàlisis de correlacions revelen que sentir-se català no impedeix sentir-se part de la comunitat etnocultural d’origen. A més, existeix una interrelació entre l'orientació cultural catalana i la identificació amb les comunitats cíviques locals. De la mateixa manera, tenir competències en llengua catalana no va en detriment de les competències en llengua castellana. Les anàlisis també mostren que factors com l’orientació cultural catalana, l’ús del català i la identificació amb la cultura catalana tenen una correlació positiva amb el grau de chohesio de la indentitat bicultural, afavoreixen el benestar psicològic i disminueixen l’estrès aculturatiu. L’anàlisi de les xarxes socials mostra que la identificació amb la cultura catalana, l’orientació cultural catalana i la integració de la identitat són factors clau per tenir xarxes socials més diverses des del punt de vista ètnic i lingüístic, amb menys membres del col•lectiu d’origen, i amb subgrups o “cliques” culturalment més heterogenis. La identificació espanyola també prediu, en mesura més reduïda, la diversitat de les xarxes. Els nostres resultats contribueixen a la recerca actual i les teories sobre interculturalitat i identitat cultural.