22 resultados para C1-symmetric N-heterocyclic carbenes

em Consorci de Serveis Universitaris de Catalunya (CSUC), Spain


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In this paper we consider C1 vector fields X in R3 having a “generalized heteroclinic loop” L which is topologically homeomorphic to the union of a 2–dimensional sphere S2 and a diameter connecting the north with the south pole. The north pole is an attractor on S2 and a repeller on . The equator of the sphere is a periodic orbit unstable in the north hemisphere and stable in the south one. The full space is topologically homeomorphic to the closed ball having as boundary the sphere S2. We also assume that the flow of X is invariant under a topological straight line symmetry on the equator plane of the ball. For each n ∈ N, by means of a convenient Poincar´e map, we prove the existence of infinitely many symmetric periodic orbits of X near L that gives n turns around L in a period. We also exhibit a class of polynomial vector fields of degree 4 in R3 satisfying this dynamics.

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We report on a series of experiments that examine bidding behavior in first-price sealed bid auctions with symmetric and asymmetric bidders. To study the extent of strategic behavior, we use an experimental design that elicits bidders' complete bid functions in each round (auction) of the experiment. In the aggregate, behavior is consistent with the basic equilibrium predictions for risk neutral or homogenous risk averse bidders (extent of bid shading, average seller's revenues and deviations from equilibrium). However, when we look at the extent of best reply behavior and the shape of bid functions, we find that individual behavior is not in line with the received equilibrium models, although it exhibits strategic sophistication.

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We study planar central configurations of the five-body problem where three of the bodies are collinear, forming an Euler central configuration of the three-body problem, and the two other bodies together with the collinear configuration are in the same plane. The problem considered here assumes certain symmetries. From the three bodies in the collinear configuration, the two bodies at the extremities have equal masses and the third one is at the middle point between the two. The fourth and fifth bodies are placed in a symmetric way: either with respect to the line containing the three bodies, or with respect to the middle body in the collinear configuration, or with respect to the perpendicular bisector of the segment containing the three bodies. The possible stacked five-body central configurations satisfying these types of symmetries are: a rhombus with four masses at the vertices and a fifth mass in the center, and a trapezoid with four masses at the vertices and a fifth mass at the midpoint of one of the parallel sides.

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We characterize the class of strategy-proof social choice functions on the domain of symmetric single-peaked preferences. This class is strictly larger than the set of generalized median voter schemes (the class of strategy-proof and tops-only social choice functions on the domain of single-peaked preferences characterized by Moulin (1980)) since, under the domain of symmetric single-peaked preferences, generalized median voter schemes can be disturbed by discontinuity points and remain strategy-proof on the smaller domain. Our result identifies the specific nature of these discontinuities which allow to design non-onto social choice functions to deal with feasibility constraints.

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We describe a model structure for coloured operads with values in the category of symmetric spectra (with the positive model structure), in which fibrations and weak equivalences are defined at the level of the underlying collections. This allows us to treat R-module spectra (where R is a cofibrant ring spectrum) as algebras over a cofibrant spectrum-valued operad with R as its first term. Using this model structure, we give sufficient conditions for homotopical localizations in the category of symmetric spectra to preserve module structures.

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Report for the scientific sojourn at the the Philipps-Universität Marburg, Germany, from september to december 2007. For the first, we employed the Energy-Decomposition Analysis (EDA) to investigate aromaticity on Fischer carbenes as it is related through all the reaction mechanisms studied in my PhD thesis. This powerful tool, compared with other well-known aromaticity indices in the literature like NICS, is useful not only for quantitative results but also to measure the degree of conjugation or hyperconjugation in molecules. Our results showed for the annelated benzenoid systems studied here, that electron density is more concentrated on the outer rings than in the central one. The strain-induced bond localization plays a major role as a driven force to keep the more substituted ring as the less aromatic. The discussion presented in this work was contrasted at different levels of theory to calibrate the method and ensure the consistency of our results. We think these conclusions can also be extended to arene chemistry for explaining aromaticity and regioselectivity reactions found in those systems.In the second work, we have employed the Turbomole program package and density-functionals of the best performance in the state of art, to explore reaction mechanisms in the noble gas chemistry. Particularly, we were interested in compounds of the form H--Ng--Ng--F (where Ng (Noble Gas) = Ar, Kr and Xe) and we investigated the relative stability of these species. Our quantum chemical calculations predict that the dixenon compound HXeXeF has an activation barrier for decomposition of 11 kcal/mol which should be large enough to identify the molecule in a low-temperature matrix. The other noble gases present lower activation barriers and therefore are more labile and difficult to be observable systems experimentally.

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Objetivo. Analizar los resultados de la fijación transarticular e interarticular en dos series de pacientes. Métodos. Se analizaron 36 pacientes con inestabilidad C1-C2, 20 tratados mediante fijación transarticular, y 15 con fijación interarticular. Se obtuvieron datos sobre las complicaciones, evolución radiológica y resultados clínicos. Resultados. De los tratados con fijación transarticular se obtuvieron resultados buenos en 17 casos, regular en 2 y malo en 1. En la fijación interarticular en 14 se obtuvieron un buen resultado, y regular en 2. Conclusiones. La fijación C1-C2 transarticular e interarticular resulta segura, con presentando altas tasas de buenos resultados con pocas complicaciones.

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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

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Graphical displays which show inter--sample distances are importantfor the interpretation and presentation of multivariate data. Except whenthe displays are two--dimensional, however, they are often difficult tovisualize as a whole. A device, based on multidimensional unfolding, isdescribed for presenting some intrinsically high--dimensional displays infewer, usually two, dimensions. This goal is achieved by representing eachsample by a pair of points, say $R_i$ and $r_i$, so that a theoreticaldistance between the $i$-th and $j$-th samples is represented twice, onceby the distance between $R_i$ and $r_j$ and once by the distance between$R_j$ and $r_i$. Self--distances between $R_i$ and $r_i$ need not be zero.The mathematical conditions for unfolding to exhibit symmetry are established.Algorithms for finding approximate fits, not constrained to be symmetric,are discussed and some examples are given.

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In this paper, we present a model of a symmetric Brownian motor which changes the sign of its velocity when the temperature gradient is inverted. The velocity, external work, and efficiency are studied as a function of the temperatures of the baths and other relevant parameters. The motor shows a current reversal when another parameter (a phase shift) is varied. Analytical predictions and results from numerical simulations are performed and agree very well. Generic properties of this type of motor are discussed.

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The issue of de Sitter invariance for a massless minimally coupled scalar field is examined. Formally, it is possible to construct a de Sitterinvariant state for this case provided that the zero mode of the field is quantized properly. Here we take the point of view that this state is physically acceptable, in the sense that physical observables can be computed and have a reasonable interpretation. In particular, we use this vacuum to derive a new result: that the squared difference between the field at two points along a geodesic observers spacetime path grows linearly with the observers proper time for a quantum state that does not break de Sitter invariance. Also, we use the Hadamard formalism to compute the renormalized expectation value of the energy-momentum tensor, both in the O(4)-invariant states introduced by Allen and Follaci, and in the de Sitterinvariant vacuum. We find that the vacuum energy density in the O(4)-invariant case is larger than in the de Sitterinvariant case.

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The infinitesimal transformations that leave invariant a two-covariant symmetric tensor are studied. The interest of these symmetry transformations lays in the fact that this class of tensors includes the energy-momentum and Ricci tensors. We find that in most cases the class of infinitesimal generators of these transformations is a finite dimensional Lie algebra, but in some cases exhibiting a higher degree of degeneracy, this class is infinite dimensional and may fail to be a Lie algebra. As an application, we study the Ricci collineations of a type B warped spacetime.

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In this paper we will find a continuous of periodic orbits passing near infinity for a class of polynomial vector fields in R3. We consider polynomial vector fields that are invariant under a symmetry with respect to a plane and that possess a “generalized heteroclinic loop” formed by two singular points e+ and e− at infinity and their invariant manifolds � and . � is an invariant manifold of dimension 1 formed by an orbit going from e− to e+, � is contained in R3 and is transversal to . is an invariant manifold of dimension 2 at infinity. In fact, is the 2–dimensional sphere at infinity in the Poincar´e compactification minus the singular points e+ and e−. The main tool for proving the existence of such periodic orbits is the construction of a Poincar´e map along the generalized heteroclinic loop together with the symmetry with respect to .

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For polynomial vector fields in R3, in general, it is very difficult to detect the existence of an open set of periodic orbits in their phase portraits. Here, we characterize a class of polynomial vector fields of arbitrary even degree having an open set of periodic orbits. The main two tools for proving this result are, first, the existence in the phase portrait of a symmetry with respect to a plane and, second, the existence of two symmetric heteroclinic loops.