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

One- and two-center physical space partitioning of the energy in the density functional theory

A conceptually new approach is introduced for the decomposition of the molecular energy calculated at the density functional theory level of theory into sum of one- and two-atomic energy components, and is realized in the "fuzzy atoms" framework. (Fuzzy atoms mean that the three-dimensional physical space is divided into atomic regions having no sharp boundaries but exhibiting a continuous transition from one to another.) The new scheme uses the new concept of "bond order density" to calculate the diatomic exchange energy components and gives them unexpectedly close to the values calculated by the exact (Hartree-Fock) exchange for the same Kohn-Sham orbitals

N-dimensional dynamical systems exploiting instabilities in full

We report experimental and numerical results showing how certain N-dimensional dynamical systems are able to exhibit complex time evolutions based on the nonlinear combination of N-1 oscillation modes. The experiments have been done with a family of thermo-optical systems of effective dynamical dimension varying from 1 to 6. The corresponding mathematical model is an N-dimensional vector field based on a scalar-valued nonlinear function of a single variable that is a linear combination of all the dynamic variables. We show how the complex evolutions appear associated with the occurrence of successive Hopf bifurcations in a saddle-node pair of fixed points up to exhaust their instability capabilities in N dimensions. For this reason the observed phenomenon is denoted as the full instability behavior of the dynamical system. The process through which the attractor responsible for the observed time evolution is formed may be rather complex and difficult to characterize. Nevertheless, the well-organized structure of the time signals suggests some generic mechanism of nonlinear mode mixing that we associate with the cluster of invariant sets emerging from the pair of fixed points and with the influence of the neighboring saddle sets on the flow nearby the attractor. The generation of invariant tori is likely during the full instability development and the global process may be considered as a generalized Landau scenario for the emergence of irregular and complex behavior through the nonlinear superposition of oscillatory motions

Variational principles for nonlinear dynamical systems

A variational method for Hamiltonian systems is analyzed. Two different variationalcharacterization for the frequency of nonlinear oscillations is also suppliedfor non-Hamiltonian systems

Fronts from complex two-dimensional dispersal kernels: theory and application to Reid's paradox

Bimodal dispersal probability distributions with characteristic distances differing by several orders of magnitude have been derived and favorably compared to observations by Nathan [Nature (London) 418, 409 (2002)]. For such bimodal kernels, we show that two-dimensional molecular dynamics computer simulations are unable to yield accurate front speeds. Analytically, the usual continuous-space random walks (CSRWs) are applied to two dimensions. We also introduce discrete-space random walks and use them to check the CSRW results (because of the inefficiency of the numerical simulations). The physical results reported are shown to predict front speeds high enough to possibly explain Reid's paradox of rapid tree migration. We also show that, for a time-ordered evolution equation, fronts are always slower in two dimensions than in one dimension and that this difference is important both for unimodal and for bimodal kernels

La teoría de Morales-Ramis y el algoritmo de Kovacic

La teor\'\ı a de Morales–Ramis es la teor\'\ı a de Galois en el contextode los sistemas din\'amicos y relaciona dos tipos diferentes de integrabilidad:integrabilidad en el sentido de Liouville de un sistema hamiltonianoe integrabilidad en el sentido de la teor\'\ı a de Galois diferencial deuna ecuaci\'on diferencial. En este art\'\i culo se presentan algunas aplicacionesde la teor\'\i a de Morales–Ramis en problemas de no integrabilidadde sistemas hamiltonianos cuya ecuaci\'on variacional normal a lo largode una curva integral particular es una ecuaci\'on diferencial lineal desegundo orden con coeficientes funciones racionales. La integrabilidadde la ecuaci\'on variacional normal es analizada mediante el algoritmode Kovacic.

Rational Partisan Theory with fiscal policy and an independent central bank

The empirical evidence testing the validity of the rational partisan theory (RPT) has been mixed. In this article, we argue that the inclusion of other macroeconomic policies and the presence of an independent central bank can partly contribute to explain this inconclusiveness. This article expands Alesina s (1987) RPT model to include an extra policy and an independent central bank. With these extensions, the implications of RPT are altered signi ficantly. In particular, when the central bank is more concerned about output than public spending (an assumption made by many papers in this literature), then the direct relationship between in flation and output derived in Alesina (1987) never holds. Keywords: central bank, conservativeness, political uncertainty. JEL Classi fication: E58, E63.

The Big Band Theory : català col·loquial i humor científic. Proposta de traducció del capítol pilot

Aquest treball elabora una proposta de traducció per al doblatge del capítol pilot de The Big Bang Theory, que combina llenguatge col•loquial i llenguatge científic.L’objectiu és doble: elaborar un llenguatge col•loquial creïble però a la vegada genuí i emprar els equivalents catalans adequats per als termes científics originals.

Capital, Wages, and Growth: Theory and Evidence

Returns to scale to capital and the strength of capital externalities play a key role for the empirical predictions and policy implications of different growth theories. We show that both can be identified with individual wage data and implement our approach at the city-level using US Census data on individuals in 173 cities for 1970, 1980, and 1990. Estimation takes into account fixed effects, endogeneity of capital accumulation, and measurement error. We find no evidence for human or physical capital externalities and decreasing aggregate returns to capital. Returns to scale to physical and human capital are around 80 percent. We also find strong complementarities between human capital and labor and substantial total employment externalities.

Measurement with Some Theory: a New Approach to Evaluate Business Cycle Models

We propose a method to evaluate cyclical models which does not require knowledge of the DGP and the exact empirical specification of the aggregate decision rules. We derive robust restrictions in a class of models; use some to identify structural shocks and others to evaluate the model or contrast sub-models. The approach has good size and excellent power properties, even in small samples. We show how to examine the validity of a class of models, sort out the relevance of certain frictions, evaluate the importance of an added feature, and indirectly estimate structural parameters.

Social Security in Theory and Practice (II): Efficiency Theories, Narrative Theories, and Implications for Reform

166 countries have some kind of public old age pension. What economic forces create and sustain old age Social Security as a public program? Mulligan and Sala-i-Martin (1999b) document several of the internationally and historically common features of social security programs, and explore "political" theories of Social Security. This paper discusses the "efficiency theories", which view creation of the SS program as a full of partial solution to some market failure. Efficiency explanations of social security include the "SS as welfare for the elderly" the "retirement increases productivity to optimally manage human capital externalities", "optimal retirement insurance", the "prodigal father problem", the "misguided Keynesian", the "optimal longevity insurance", the "government economizing transaction costs", and the "return on human capital investment". We also analyze four "narrative" theories of social security: the "chain letter theory", the "lump of labor theory", the "monopoly capitalism theory", and the "Sub-but-Nearly-Optimal policy response to private pensions theory". The political and efficiency explanations are compared with the international and historical facts and used to derive implications for replacing the typical pay-as-you-go system with a forced savings plan. Most of the explanations suggest that forced savings does not increase welfare, and may decrease it.