Two complementary molecular energy decomposition schemes: the Mayer and Ziegler-Rauk methods in comparison

In the present paper we discuss and compare two different energy decomposition schemes: Mayer's Hartree-Fock energy decomposition into diatomic and monoatomic contributions [Chem. Phys. Lett. 382, 265 (2003)], and the Ziegler-Rauk dissociation energy decomposition [Inorg. Chem. 18, 1558 (1979)]. The Ziegler-Rauk scheme is based on a separation of a molecule into fragments, while Mayer's scheme can be used in the cases where a fragmentation of the system in clearly separable parts is not possible. In the Mayer scheme, the density of a free atom is deformed to give the one-atom Mulliken density that subsequently interacts to give rise to the diatomic interaction energy. We give a detailed analysis of the diatomic energy contributions in the Mayer scheme and a close look onto the one-atom Mulliken densities. The Mulliken density ρA has a single large maximum around the nuclear position of the atom A, but exhibits slightly negative values in the vicinity of neighboring atoms. The main connecting point between both analysis schemes is the electrostatic energy. Both decomposition schemes utilize the same electrostatic energy expression, but differ in how fragment densities are defined. In the Mayer scheme, the electrostatic component originates from the interaction of the Mulliken densities, while in the Ziegler-Rauk scheme, the undisturbed fragment densities interact. The values of the electrostatic energy resulting from the two schemes differ significantly but typically have the same order of magnitude. Both methods are useful and complementary since Mayer's decomposition focuses on the energy of the finally formed molecule, whereas the Ziegler-Rauk scheme describes the bond formation starting from undeformed fragment densities

On Rothschild-Stiglitz as competitive pooling

Dubey and Geanakoplos [2002] have developed a theory of competitive pooling, which incorporates adverse selection and signaling into general equilibrium. By recasting the Rothschild-Stiglitz model of insurance in this framework, they find that a separating equilibrium always exists and is unique.We prove that their uniqueness result is not a consequence of the framework, but rather of their definition of refined equilibria. When other types of perturbations are used, the model allows for many pooling allocations to be supported as such: in particular, this is the case for pooling allocations that Pareto dominate the separating equilibrium.

La influencia de la Constitución Española de 1812 en el constitucionalismo chileno del s. XIX. Un análisis comparado

Aquest treball presenta un anàlisi comparat de la Constitució espanyola de 1812 i les diverses constitucions xilenes del segle XIX. L’objectiu és determinar la influència d’una constitució vigent en ambdós territoris al desenvolupament constitucionalisme xilè posterior. L’estudi es realitza des de tres perspectives: institucional, estructural i literal.

El proceso electoral en España y Cataluña según la Constitución de 1812

En el presente trabajo se analiza la normativa electoral y su aplicación incluida en el articulado de la Constitución de 1812. Para ello en primer lugar se estudia el espíritu del proyecto electoral constitucional. Posteriormente se analiza su aplicación en los comicios para elegir las Cortes Ordinarias de 1813 en las dos realidades que contempla: los territorios de la metrópoli y los de ultramar. Analizada la normativa electoral, establecemos el Parlamento teórico resultante y su aplicación real. Finalmente, realizamos un análisis prosopográfico de los diputados elegidos en España y Cataluña, establecemos la morfología del parlamentario tipo y lo comparamos con los resultados de las dos realidades electorales apuntadas.

Friedman's Excess energy and the McMillan-Mayer theory of solutions:Thermodynamics

In his version of the theory of multicomponent systems, Friedman used the analogy which exists between the virial expansion for the osmotic pressure obtained from the McMillan-Mayer (MM) theory of solutions in the grand canonical ensemble and the virial expansion for the pressure of a real gas. For the calculation of the thermodynamic properties of the solution, Friedman proposed a definition for the"excess free energy" that is a reminder of the ancient idea for the"osmotic work". However, the precise meaning to be attached to his free energy is, within other reasons, not well defined because in osmotic equilibrium the solution is not a closed system and for a given process the total amount of solvent in the solution varies. In this paper, an analysis based on thermodynamics is presented in order to obtain the exact and precise definition for Friedman"s excess free energy and its use in the comparison with the experimental data.