A first-principles analysis of the magnetism of CuII polynuclear coordination complexes: the case of [Cu4(bpy)4(aspartate)2(H2O)3](ClO4)4·2.5H2O

The magnetic structure of the [Cu4(bpy)4(aspartate)2(H2O)3](ClO4)4·2.5 H2Ocrystal - using fractional coordinates determined at room-temperature ¿ has beenanalysed in detail. This analysis has been carried out by extending our first principlesbottom-up theoretical approach, which was initially designed to study through-spacemagnetic interactions, to handle through-bond magnetic interactions. The only input datarequired by this approach are the values of the computed JAB exchange parameters for allthe unique pairs of spin-containing centres. The results allow the magnetic structure ofthe crystal, which presents two types of isolated tetranuclear CuII clusters, to be definedin quantitative terms. Each of these clusters presents ferro and antiferromagneticinteractions, the former being stronger, although outnumbered by the latter. Thecomputed magnetic susceptibility curve shows the same qualitative features as theexperimental data. However, there are small differences that are presumed to beassociated with the use of room-temperature crystal coordinates.

A first-principles analysis of the magnetism of CuII polynuclear coordination complexes: the case of [Cu4(bpy)4(aspartate)2(H2O)3](ClO4)4·2.5H2O

The magnetic structure of the [Cu4(bpy)4(aspartate)2(H2O)3](ClO4)4·2.5 H2Ocrystal - using fractional coordinates determined at room-temperature ¿ has beenanalysed in detail. This analysis has been carried out by extending our first principlesbottom-up theoretical approach, which was initially designed to study through-spacemagnetic interactions, to handle through-bond magnetic interactions. The only input datarequired by this approach are the values of the computed JAB exchange parameters for allthe unique pairs of spin-containing centres. The results allow the magnetic structure ofthe crystal, which presents two types of isolated tetranuclear CuII clusters, to be definedin quantitative terms. Each of these clusters presents ferro and antiferromagneticinteractions, the former being stronger, although outnumbered by the latter. Thecomputed magnetic susceptibility curve shows the same qualitative features as theexperimental data. However, there are small differences that are presumed to beassociated with the use of room-temperature crystal coordinates.

Invoking a cartesian product structure on social states: new resolutions of Sen's and Gibbard's impossibility theorems

The purpose of this article is to introduce a Cartesian product structure into the social choice theoretical framework and to examine if new possibility results to Gibbard's and Sen's paradoxes can be developed thanks to it. We believe that a Cartesian product structure is a pertinent way to describe individual rights in the social choice theory since it discriminates the personal features comprised in each social state. First we define some conceptual and formal tools related to the Cartesian product structure. We then apply these notions to Gibbard's paradox and to Sen's impossibility of a Paretian liberal. Finally we compare the advantages of our approach to other solutions proposed in the literature for both impossibility theorems.

Observability and overcoming coordination failure in organizations

Many organizations suffer poor performance because its members fail to coordinate on efficient patterns of behavior. In previous research, we have shown that financial incentives can be used to find a way out of such performance traps. Here we examine the sensitivity of this result to the ability of people to observe others' choices. Our experiments are set in a corporate environment where subjects' payoffs depend on coordinating at high effort levels; the underlying game being played repeatedly by the employees of an experimental firm is a weak-link game. Treatments vary along two dimensions. First, subjects either start with low financial incentives for coordination, which typically leads to coordination failure, and then are switched to higher incentives or start with high incentives, which typically yield effective coordination, and are switched to low incentives. Second, as the key treatment variable, subjects either observe the effort levels chosen by all employees in their experimenta

A change would do you good . . . An experimental study on how to overcome coordination failure in organizations

Many organizations suffer poor performance because individuals within the organization fail to coordinate on efficient patterns of behavior. Using controlled laboratory experiments, we study how financial incentives can be used to find a way out of such performance traps. Our experiments are set in a corporate environment where subjects' payoffs depend on coordinating at high effort levels; the underlying game being played repeatedly by employees is a weak-link game. In an initial phase, the benefits of coordination are low relative to the cost of increased effort. Play in this initial phase typically converges to an inefficient outcome with employees failing to coordinate at high effort levels. The experimental design then explores the effects of varying the financial incentives to coordinate at a higher effort level. We find that an increase in the benefits of coordination leads to improved coordination, but, surprisingly, large increases have no more impact than small increases. Once subj

Urban spatial structure and suburbanisation. The case of the Barcelona Metropolitan

The metropolitan spatial structure displays various patterns, sometimes monocentricity and sometimes multicentricity, which seems much more complicated than the exponential density function used in classic works such as Clark (1961), Muth (1969) or Mills (1973) among others, can effectively represent. It seems that a more flexible density function,such as cubic spline function (Anderson (1982), Zheng (1991), etc.) to describe the density-accessibility relationship is needed. Also, accessibility, the fundamental determinant of density variations, is only partly captured by the inclusion of distance to the city centre as an explanatory variable. Steen (1986) has proposed to correct that miss-especification by including an additional gradient for distance to the nearest transportation axis. In identifying the determinants of urban spatial structure in the context of inter-urban systems, some of the variables proposed by Muth (1969), Mills (1973) and Alperovich (1983) such as city age or population, make no sense in the case of a single urban system. All three criticism to the exponential density function and its determinants apply for the Barcelona Metropolitan Region, a polycentric conurbation structured on well defined transportation axes.

Airline competition and network structure

This paper characterizes the equilibria in airline networks and their welfare implications in an unregulated environment. Competing airlines may adopt either fully-connected (FC) or hub-and-spoke (HS) network structures; and passengers exhibiting low brand loyalty to their preferred carrier choose an outside option to travel so that markets are partially served by airlines. In this context, carriers adopt hubbing strategies when costs are sufficiently low, and asymmetric equilibria where one carrier chooses a FC strategy and the other chooses a HS strategy may arise. Quite interestingly, flight frequency can become excessive under HS network configurations.

Organisational structure, communication and group ethics

This paper investigates experimentally how organisational decision processes affect the moral motivations of actors inside a firm that must forego profits to reduce harming a third party. In a "vertical" treatment, one insider unilaterally sets the harm-reduction strategy; the other can only accept or quit. In a "horizontal" treatment, the insiders decide by consensus. Our 2-by-2 design also controls for communication effects. In our data, communication makes vertical firms more ethical; voice appears to mitigate "responsibility-alleviation" in that subordinates with voice feel responsible for what their firms do. Vertical firms are then more ethical than the horizontal firms for which our bargaining data reveal a dynamic form of responsibility-alleviation and our chat data indicate a strong "insider-outsider" effect.

Leadership and overcoming coordination failure with asymmetric costs

We study how the heterogeneity of agents affects the extent to which changes in financial incentives can pull a group out of a situation of coordination failure. We focus on the connections between cost asymmetries and leadership. Experimental subjects interact in groups of four in a series of weak-link games. The treatment variable is the distribution of high and low effort cost across subjects. We present data for one, two and three low-cost subjects as well as control sessions with symmetric costs. The overall pattern of coordination improvement is common across treatments. Early coordination improvements depend on the distribution of high and low effort costs across subjects, but these differences disappear with time. We find that initial leadership in overcoming coordination failure is not driven by low-cost subjects but by subjects with the most frequent cost. This conformity effect can be due to a kind of group identity or to the cognitive simplicity of acting with identical others.

Debt and deficit fluctuations and the structure of bond markets

We analyse the implications of optimal taxation for the stochastic behaviour of debt. We show that when a government pursues an optimal fiscal policy under complete markets, the value of debt has the same or less persistence than other variables in the economy and it declines in response to shocks that cause the deficit to increase. By contrast, under incomplete markets debt shows more persistence than other variables and it increases in response to shocks that cause a higher deficit. Data for US government debt reveals diametrically opposite results from those of complete markets and is much more supportive of bond market incompleteness.

A model category structure on the category of simplicial multicategories

We establish a Quillen model structure on simplicial(symmetric) multicategories. It extends the model structure on simplicial categories due to J. Bergner [2]. We observe that our technique of proof enables us to prove a similar result for (symmetric) multicategories enriched over other monoidal model categories than simplicial sets. Examples include small categories, simplicial abelian groups and compactly generated Hausdorff spaces.

A Thomason model structure on the category of small n-fold categories

We construct a cofibrantly generated Thomason model structure on the category of small n-fold categories and prove that it is Quillen equivalent to the standard model structure on the category of simplicial sets. An n-fold functor is a weak equivalence if and only if the diagonal of its n-fold nerve is a weak equivalence of simplicial sets. We introduce an n-fold Grothendieck construction for multisimplicial sets, and prove that it is a homotopy inverse to the n-fold nerve. As a consequence, the unit and counit of the adjunction between simplicial sets and n-fold categories are natural weak equivalences.

Mecanismes de reacció de sistemes catalítics amb èmfasi en carbens de Fischer i quantificació de l'aromaticitat en petites molècules inorgàniques cícliques i planes.

El tema principal del treball és sobre l'estudi teòric de l'estructura i reactivitat en carbens de Fischer de la forma (CO)5Cr=C(X)R (X= OH, NH2, OMe, NMe2 i R= CHCH2 i Ph). Particularment, el nostre interès va sorgir del tipus de reaccions de cicloadicció que donen lloc a la síntesi de productes naturals i fàrmacs de gran valor afegit. Hem estudiat els mecanismes de reacció dels casos més comuns de cicloanul•lació: la reacció de benzanul•lació de Dötz i ciclopentanulacions que es troben en competència amb el primer cas, derivats de l'inserció de acetilè i fenilacetilè. En l'últim pas de les reaccions que comporten la formació d'un sistema de més d'un anell, hi tenim una migració del complex metàl•lic de crom d'un extrem a un altre anomenat com rearranjament haptotròpic. Aleshores, hem investigat sobre els mecanismes de migració haptotròpica de Cr(CO)3 sobre hidrocarburs aromàtics policíclics analitzant l'efecte de la mida i la curvatura del sistema així com la complexació d'un segon fragment metàl•lic a la manera de coordinació als anells. D'una altre banda, vam estudiar l'aromaticitat en 54 cúmuls cíclics de molecules inorgàniques mitjançant metodologia desenvolupada al nostre grup de recerca i altres. Vam proposar la tècnica del scan-NICS com nova mesura quantitativa d'aromaticitat i reportar l'escassa correlació entre els distints índexs d'aromaticitat a la literatura. Finalment, com resultat de col•laboracions en estades de recerca, he desenvolupat propostes de mecanismes de reacció en sistemes catalítics de isonitrils i fosfinetà-amides i en dímers de gassos nobles.

The Accessibility City. When Transport Infrastructure Matters in Urban Spatial Structure

Suburbanization is changing the urban spatial structure and less monocentric metropolitan regions are becoming the new urban reality. Focused only on centers, most works have studied these spatial changes neglecting the role of transport infrastructure and its related location model, the “accessibility city”, in which employment and population concentrate in low-density settlements and close to transport infrastructure. For the case of Barcelona, we consider this location model and study the population spatial structure between 1991 and 2006. The results reveal a mix between polycentricity and the accessibility city, with movements away from the main centers, but close to the transport infrastructure.

Structure theorems for subgroups of homeomorphism groups

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