Multistep reaction analysis. A numerical approach based on relaxation theory

A general numerical method and program for simulation of the kinetics of multistep reactions is described, with details for collation of data, construction of a mechanistic model, and simulation of reciprocal relaxation times and calculation of individual rate constants. The working scheme of the program includes an initial approximate simulation by adjustment of the rate constants followed by their optimization with a Powell minimization subroutine. The procedure is applied to aromatic nucleophilic addition.     

A new algorithm that generates the image of the attractor of a generalized iterated function system

Numerical Algorithms - We provide a new algorithm (called the grid algorithm) designed to generate the image of the attractor of a generalized iterated function system on a finite dimensional space...     

Unsteady Flow and its Influence to Aerodynamic and Aeroacoustic of VAWT's

A study is reported of the influence of unsteady flow on the aerodynamics and aeroacoustics of vertical axis wind turbines by numerical simulation. The combination of aerodynamic predictions with a discrete vortex method and aeroacoustic predictions based on Ffowcs Williams-Hawkings equation is used to achieve this goal. The numerical results show that unsteady flow of the turbine has a significant influence on the turbine aerodynamics and can lead to a decrease in generated noise as compared to the conventional horizontal axis wind turbine at the similar aerodynamic performance. (© 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Conformational Effects of Regioisomeric Substitution on the Catalytic Activity of Copper/Calix[8]arene C−S Coupling

Functionalization of the phenolic rim of p-tert-butylcalix[8]arene with phenanthroline to create a cavity leads to formation of two regioisomers. Substitution of positions 1 and 5 produces the known C_2v-symmetric regioisomer 1,5-(2,9-dimethyl-1,10-phenanthroyl)-p-tert-butylcalix[8]arene ( L^1,5 ), while substitution of positions 1 and 4 produces the C_s-symmetric regioisomer 1,4-(2,9-dimethyl-1,10-phenanthroyl)-p-tert-butylcalix[8]arene ( L^1,4 ) described herein. [ Cu(L^1,4)I ] was synthesized from L^1,4 and CuI in good yield and characterized spectroscopically. To evaluate the effect of its cavity on catalysis, Ullmann-type C−S coupling was chosen as proof-of-concept. Selected aryl halides were used, and the results compared with the previously reported Cu(I)/ L^1,5 system. Only highly activated aryl halides generate the C−S coupling product in moderate yields with the Cu(I)/ L^1,4 system. To shed light on these observations, detailed computational investigations were carried out, revealing the influence of the calix[8]arene macrocyclic morphology on the accessible conformations. The L^1,4 regioisomer undergoes a deformation that does not occur with L^1,5 , resulting in an exposed catalytic center, presumably the cause of the low activity of the former system. The 1,4-connectivity was confirmed in the solid-state structure of the byproduct [ Cu(L^1,4 − H) (CH₃CN)₂] that features Cu(I) coordinated inside a cleft defined by the macrocyclic framework.     

Nash-Type Equilibria for Systems of Szulkin Functionals

In this paper the solutions of some systems of variational inequalities are obtained as Nash-type equilibria of the corresponding systems of Szulkin functionals. This is achieved by an iterative scheme based on Ekeland’s variational principle, whose convergence is proved via the vector technique involving inverse-positive matrices. An application to periodic solutions for a system of two second order ordinary differential equations with singular ?-Laplacians is included.     

Neutron resonances in planar waveguides

We report on the results of the experimental investigation of the spectral width of neutron resonances in planar waveguides using the time-of-flight method and recording the microbeam emerging from the waveguide end. Experimental data are compared with the results of theoretical calculations.