Theoretical and empirical differentiations of phases in the modelling process

The reconstruction of pupils modelling processes can be found in many empirical studies within the literature on modelling. The empirical differentiations of the phases, which includes putting statements and actions of the pupils in the right phase, has not been reconstructed from a cognitive psychological point of view on a micro level thus far: In this article different modelling cycles are discussed with attention to distinctions in the various phases. The «modelling cycle under cognitive psychological aspects» is specifically emphasized in contrast to the other cycles. On the basis of the results of the COM²-project (Cognitive psychological analysis of modelling processes in mathematics lessons, Borromeo Ferri) the phases of the modelling processare described empirically. Some difficulties in the process of distinguishing the various phases are also pointed out.     

Theoretical and spectroscopic study of the effect of ring substitution on the adsorption of anisole on platinum

The adsorption of anisole, 3,5-dimethylanisole, and 3,5-bis-(trifluoromethyl)-anisole on Pt(111) was studied theoretically and compared to the adsorption of benzene using relativistically corrected density functional theory. A cluster of 31 platinum atoms was used to simulate the surface. The three anisoles were found to be less strongly adsorbed than the parent molecule benzene, 3,5-bis-(trifluoromethyl)-anisole showing weakest adsorption, with an adsorption energy of only one-third that of benzene. The theoretical study was complemented by in situ ATR-IR spectroscopy of the adsorption of the anisole derivatives on a polycrystalline Pt film. The spectroscopic study indicated that the adsorption strength of the anisoles follows the same order as predicted by the calculations. In addition, catalytic hydrogenation tests showed that the propensity to aromatic ring hydrogenation can also be correlated to the mode and strength of adsorption of the anisoles. The degree of saturation followed the same order as the adsorption strength found by the calculations and indicated by spectroscopy. Although 3,5-dimethyl substitution on anisole resulted in only a partial loss of adsorption energy and reactivity toward ring hydrogenation as compared to anisole, the substitution by CF(3) groups led to a large loss of adsorption energy and complete loss of reactivity toward aromatic ring saturation. Along with the study of the substituent effect on the adsorption of aromatic molecules, the correlation between adsorption and propensity to saturation of aromatic substrates could be corroborated.     

A Bayesian Networks approach to Operational Risk

A system for Operational Risk management based on the computational paradigm of Bayesian Networks is presented. The algorithm allows the construction of a Bayesian Network targeted for each bank and takes into account in a simple and realistic way the correlations among different processes of the bank. The internal losses are averaged over a variable time horizon, so that the correlations at different times are removed, while the correlations at the same time are kept: the averaged losses are thus suitable to perform the learning of the network topology and parameters; since the main aim is to understand the role of the correlations among the losses, the assessments of domain experts are not used. The algorithm has been validated on synthetic time series. It should be stressed that the proposed algorithm has been thought for the practical implementation in a mid or small sized bank, since it has a small impact on the organizational structure of a bank and requires an investment in human resources which is limited to the computational area.     

A Diffusive Strategic Dynamics for Social Systems

We propose a model for the dynamics of a social system, which includes diffusive effects and a biased rule for spin-flips, reproducing the effect of strategic choices. This model is able to mimic some phenomena taking place during marketing or political campaigns. Using a cost function based on the Ising model defined on the typical quenched interaction environments for social systems (Erdös-Renyi graph, small-world and scale-free networks), we find, by numerical simulations, that a stable stationary state is reached, and we compare the final state to the one obtained with standard dynamics, by means of total magnetization and magnetic susceptibility. Our results show that the diffusive strategic dynamics features a critical interaction parameter strictly lower than the standard one. We discuss the relevance of our findings in social systems.     

Discrimination of active palladium sites in catalytic liquid-phase oxidation of benzyl alcohol

Knowledge of the structure of active sites is a prerequisite for the rational design of solid catalysts. Using site-selective blocking by CO and isotope labeling combined with in situ attenuated total reflection infrared (ATR-IR) spectroscopy, we were able to discriminate the different sites involved in the liquid-phase oxidation of benzyl alcohol on Pd/Al(2)O(3). The main reaction, that is, the oxidative dehydrogenation of the alcohol to the corresponding aldehyde, showed only little dependence on structure and occurred on all exposed Pd faces, whereas the undesired product decarbonylation occurred preferentially on hollow sites on (111) Pd faces. This explains why specific blocking of the latter sites, as realized in the industrially used Pd-Bi/Al(2)O(3) catalysts, leads to improved catalytic performance.     

The motion of a solid with large deformations

We study the motion of a solid with large deformations. The solid may be loaded on its surface by needles, rods, beams, plates… Therefore it is wise to choose a third-gradient theory for the body. Stretch matrix of the polar decomposition has to be symmetric. This is an internal constraint which introduces a reaction stress in the Piola–Kirchhoff–Boussinesq stress. We prove that there exists a motion that satisfies the complete equations of Mechanics in a convenient variational framework. This motion is local-in-time because it may be interrupted by crushing, resulting in a discontinuity of velocity with respect to time, i.e., an internal collision.     

Labeled sequent calculi for modal logics and implicit contractions

The paper settles an open question concerning Negri-style labeled sequent calculi for modal logics and also, indirectly, other proof systems which make (more or less) explicit use of semantic parameters in the syntax and are thus subsumed by labeled calculi, like Brünnler’s deep sequent calculi, Poggiolesi’s tree-hypersequent calculi and Fitting’s prefixed tableau systems. Specifically, the main result we prove (through a semantic argument) is that labeled calculi for the modal logics K and D remain complete w.r.t. valid sequents whose relational part encodes a tree-like structure, when the unique rule which contains an harmful implicit contraction—by which the condition that the premises be less complex than the conclusion is violated—is modified into a contraction-free one respecting the latter condition, thus making the proof-search space finite.     

Kinetic study on effect of novel cationic dimeric surfactants for the cleavage of carboxylate ester

Kinetic study has been performed to understand the reactivity of novel cationic gemini surfactants viz. alkanediyl‐α,ω‐bis(hydroxyethylmethylhexadecylammonium bromide) C₁₆‐s‐C₁₆ MEA, 2Br^? (where s = 4, 6) in the cleavage of p‐nitrophenyl benzoate (PNPB). Novel cationic gemini C₁₆‐s‐C₁₆ MEA, 2Br^? surfactants are efficient in promoting PNPB cleavage in presence of butane 2,3‐dione monoximate and N‐phenylbenzohydroxamate ions. Model calculation revealed that the higher catalytic effect of ethanol moiety of gemini surfactants (C₁₆H₃₃N⁺ C₂H₄OH CH₃ (CH₂)_S N⁺ C₂H₄OH CH₃C₁₆H₃₃, 2Br^?, s = 4, 6) is due to their higher binding capacity toward substrate. This is in line with finding that binding constants for novel series of cationic gemini surfactants are higher than conventional cationic gemini (C₁₆H₃₃N⁺(CH₃)₂(CH₂)_SN⁺(CH₃)₂C₁₆H₃₃, 2Br^?, s = 10, 12), cetyldimethylethanolammonium bromide and zwitterionic surfactants, i.e. C_nH_2n+1N⁺Me₂ (CH₂)₃ SO₃^? (n = 10; SB3‐10). The fitting of kinetic data was analyzed by the pseudophase model. Copyright © 2013 John Wiley & Sons, Ltd.     

Analysis of spectral Hamiltonian boundary value methods (SHBVMs) for the numerical solution of ODE problems

Numerical Algorithms - Recently, the numerical solution of stiffly/highly oscillatory Hamiltonian problems has been attacked by using Hamiltonian boundary value methods (HBVMs) as spectral methods...