Second Order Fit for Mercuric Chloride Catalysed Solvolysis of Alkyl Chlorides in Aqueous DMSO Solvents

Kinetics of mercuric chloride catalysed solvolysis of l-butyl chloride, benzyl chloride. p-methylbenzyl chloride, l-phenylethyl chloride and triethylcarbinyl chloride have been studied in aq. DMSO, aq. acetonitrile and aq. ethanol. The kinetic data fit a second order rate equation in aq. DMSO. The calculated values of the second order rate coefficients increase in the case of aq. acetonitrile and aq. ethanol. The order in catalyst in 95%(v/v) aq. DMSO is less than unity.

Studies of stability of fluid flowa using variational methods

The study of stability problems is relevant to the study of structure of a physical system. It 1S particularly important when it is not possible to probe into its interior and obtain information on its structure by a direct method. The thesis states about stability theory that has become of dominant importance in the study of dynamical systems. and has many applications in basic fields like meteorology, oceanography, astrophysics and geophysics- to mention few of them. The definition of stability was found useful 1n many situations, but inadequate in many others so that a host of other important concepts have been introduced in past many years which are more or less related to the first definition and to the common sense meaning of stability. In recent years the theoretical developments in the studies of instabilities and turbulence have been as profound as the developments in experimental methods. The study here Points to a new direction for stability studies based on Lagrangian formulation instead of the Hamiltonian formulation used by other authors.

An LMI approach to H∞ synchronization of second-order neutral master-slave systems

The H∞ synchronization problem of the master and slave structure of a second-order neutral master-slave systems with time-varying delays is presented in this paper. Delay-dependent sufficient conditions for the design of a delayed output-feedback control are given by Lyapunov-Krasovskii method in terms of a linear matrix inequality (LMI). A controller, which guarantees H∞ synchronization of the master and slave structure using some free weighting matrices, is then developed. A numerical example has been given to show the effectiveness of the method

The curvature of the conical intersection seam: an approximate second-order analysis

We present a method for analyzing the curvature (second derivatives) of the conical intersection hyperline at an optimized critical point. Our method uses the projected Hessians of the degenerate states after elimination of the two branching space coordinates, and is equivalent to a frequency calculation on a single Born-Oppenheimer potential-energy surface. Based on the projected Hessians, we develop an equation for the energy as a function of a set of curvilinear coordinates where the degeneracy is preserved to second order (i.e., the conical intersection hyperline). The curvature of the potential-energy surface in these coordinates is the curvature of the conical intersection hyperline itself, and thus determines whether one has a minimum or saddle point on the hyperline. The equation used to classify optimized conical intersection points depends in a simple way on the first- and second-order degeneracy splittings calculated at these points. As an example, for fulvene, we show that the two optimized conical intersection points of C2v symmetry are saddle points on the intersection hyperline. Accordingly, there are further intersection points of lower energy, and one of C2 symmetry - presented here for the first time - is found to be the global minimum in the intersection space

Second-order Møller-Plesset perturbation theory without basis set superposition error : II : open-shell systems

The basis set superposition error-free second-order MØller-Plesset perturbation theory of intermolecular interactions was studied. The difficulties of the counterpoise (CP) correction in open-shell systems were also discussed. The calculations were performed by a program which was used for testing the new variants of the theory. It was shown that the CP correction for the diabatic surfaces should be preferred to the adiabatic ones

Synthesis and characterization of thermally stable second-order nonlinear optical side-chain polyimides containing thiazole and benzothiazole push-pull chromophores

Push-pull nonlinear optical (NLO) chromophores containing thiazole and benzothiazole acceptors were synthesized and characterized. Using these chromophores a series of second-order NLO polyimides were Successfully prepared from 4,4'-(hexafluoroisopropylidene) diphthalic anhydride (6FDA), pyromellitic dianhydride (PMDA) and 3,3'4,4'-benzophenone tetracarboxylic dianhydride (BTDA) by a standard condensation polymerization technique. These polyimides exhibit high glass transition temperatures ranging from 160 to 188 degrees C. UV-vis spectrum of polyimide exhibited a slight blue shift and decreases in absorption due to birefringence. From the order parameters, it was found that chromophores were aligned effectively. Using in situ poling and temperature ramping technique, the optical temperatures for corona poling were obtained. It was found that the optimal temperatures of polyimides approach their glass transition temperatures. These polyimides demonstrate relatively large d(33) values range between 35.15 and 45.20 pm/V at 532 nm. (C) 2008 Elsevier B.V. All rights reserved.

Second order Coriolis resonance in the v2, v5 Raman bands of CH3F

The vibration-rotation Raman spectrum of the ν2 and ν5 fundamentals of CH3F is reported, from 1320 to 1640 cm−1, with a resolution of about 0.3 cm−1. The Coriolis resonance between the two bands leads to many perturbation-allowed transitions. Where the resonance is still sufficiently weak that the quantum number K′ retains its meaning, perturbation-allowed transitions are observed for all values of ΔK from +4 to −4; in regions of strong resonance, however, we can only say that the observed transitions obey the selection rule Δ(k−l) = 0 or ±3. The spectrum has been analyzed by band contour simulation using a computer program based on exact diagonalization of the Hamiltonian within the ν2, ν5 vibrational levels, and improved vibration-rotation constants for these bands are reported. The relative magnitudes and relative sings of polarizability derivatives involved in these vibrations are also reported.

Second-order cybernetics and enactive perception

Purpose - To present an account of cognition integrating second-order cybernetics (SOC) together with enactive perception and dynamic systems theory. Design/methodology/approach - The paper presents a brief critique of classical models of cognition then outlines how integration of SOC, enactive perception and dynamic systems theory can overcome some weaknesses of the classical paradigm. Findings - Presents the critique of evolutionary robotics showing how the issues of teleology and autonomy are left unresolved by this paradigm although their solution fits within the proposed framework. Research limitations/implications - The paper highlights the importance of genuine autonomy in the development of artificial cognitive systems. It sets out a framework within which the robofic research of cognitive systems could succeed. Practical implications - There are no immediate practical implications but see research implications. Originality/value - It joins the discussion on the fundamental nature of cognitive systems and emphasise the importance of autonomy and embodiment.