Aromatic molecules in restricted geometries: photophysics of naphthalene included in a cyclodextrin functionalized layered solid

The galleries of an Mg-Al layered double hydroxide have been functionalized by intercalation of carboxymethyl beta-cyclodextrin cavities. The anchored cavities form a random array of identical-sized hydrophobic nanopockets arranged in a bilayer fashion in the interlamellar space of the layered solid. Naphthalene molecules have been included within these cavities by partitioning from a polar solvent. The fluorescence from the included naphthalene shows an unusual behavior--the excimer to monomer emission intensity decreases with increasing concentration of included naphthalene. This is shown to be a consequence of the absence of translational mobility of the naphthalene--cyclodextrin adduct in the functionalized solid. Two types of included naphthalene have been identified: a preformed excimer-like species characterized by the absence of rise time in decay measurements and a monomeric species that is incapable of excimer formation due to the absence of suitably located included naphthalenes in its proximity. The concentration of each species and the enthalpy for excimer formation have been determined from the temperature variation of fluorescence intensities.     

Adsorption of n-hexane in zeolite-5A: a temperature-programmed desorption and IR-spectroscopic study

The adsorption and desorption of n-hexane over Zeolite-5A has been investigated as a function of loading using simultaneous Fourier transform infrared (FTIR)-temperature-programmed desorption (TPD) measurements. The TPD profiles show a second peak developing at lower temperatures when loading exceeds 16 hexane molecules per Zeolite-5A unit cell or two molecules per alpha-cavity of the Zeolite-5A structure. The infrared spectra rule out two types of adsorption sites as the origin of the two peaks in the TPD. Changes in the conformation of the adsorbed hexane as a function of loading and temperature were followed by monitoring the position of the methylene stretching modes in the infrared spectra. With increasing loading, the adsorbed hexane adopts a stretched trans conformation. These changes occur at loading levels below 12 hexane molecules per Zeolite-5A unit cell. No change is observed above this loading, ruling out any conformational change at loadings where the second peak is seen in the TPD. The second peak in the TPD arises, therefore, from a combination of steric repulsion and loss of translational entropy.     

High‐temperature shock tube study of the reactions CH3 + OH → products and CH3OH + Ar → products

The reaction between methyl and hydroxyl radicals has been studied in reflected shock wave experiments using narrow‐linewidth OH laser absorption. OH radicals were generated by the rapid thermal decomposition of tert‐butyl hydroperoxide. Two different species were used as CH₃ radical precursors, azomethane and methyl iodide. The overall rate coefficient of the CH₃ + OH reaction was determined in the temperature range 1081–1426 K under conditions of chemical isolation. The experimental data are in good agreement with a recent theoretical study of the reaction. The decomposition of methanol to methyl and OH radicals was also investigated behind reflected shock waves. The current measurements are in good agreement with a recent experimental study and a master equation simulation. © 2008 Wiley Periodicals, Inc. 40: 488–495, 2008     

Synthesis and Crystal Structure of a Decamethyleuropocene Complex Supported by a “Clamshell” Ligand

Abstract  

The coordination of decamethyleuropocene to a “clamshell” 1,2-bis(imino)acenaphthene (BIAN) ligand is accompanied by a one-electron redox process. The crystal structure of the Eu³⁺ product has been determined. The complex crystallizes in the triclinic space group P-1, with a = 12.065(2), b = 15.391(3), c = 17.266(4) ?, α = 73.71, β = 73.93(3), γ = 81.40(3)°, V = 2948.3(10) ?³ and Z = 2. The pyridine moiety of the clamshell ligand is not coordinated to the Eu³⁺ center.     

Nucleation kinetics,growth, solubility and dielectric studies of L‐proline cadmium chloride monohydrate semi organic nonlinear optical single crystal

Nucleation parameters such as solubility, induction period, interfacial energy and metastable zone width have been investigated for the aqueous solution growth of a semi‐organic nonlinear optical (NLO) material of L‐Proline cadmium chloride monohydrate (L‐PCCM) single crystal. Metastable zone width and induction period values were determined experimentally in order to optimize the growth parameters. The grown crystals are transparent (dimensions: 16 x 8 x 5 mm³) and characterized by powder X‐Ray Diffraction and dielectric studies. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Studies on lattice thermal expansion and XPS of ThO2NdO1.5 solid solutions

The lattice parameter changes with respect to temperature (T) have been measured by high temperature X-ray diffraction (HTXRD) technique for ThO₂NdO_1.5 solid solutions containing 23.8 and 42.5 mol% NdO_1.5 in the temperature range from 298 to 2000 K. The temperature versus lattice parameter data have been made use of in calculating the lattice thermal expansivity. The values of thermal expansion of the solid solutions were found to be increased with increase in neodymium oxide content and temperature. The mean linear thermal expansion coefficients in this temperature range for ThO₂NdO_1.5 solid solutions are 12.28 × 10⁻⁶ and 12.90 × 10⁻⁶ K⁻¹, respectively. The binding energies of Th 4f_7/2 and Nd 3d_5/2 energy levels of the solid solutions containing 13.1, 23.8, 31.9, 37.2 and 42.5 mol% NdO_1.5 and two-phase mixtures containing 47.6 and 51.8 mol% NdO_1.5 were experimentally determined by X-ray photoelectron spectroscopy (XPS).     

Computation of heat transfer enhancement in a plate‐fin heat exchanger with triangular inserts and delta wing vortex generator

Longitudinal vortices disrupt the growth of the thermal boundary layer, thereby the vortex generators producing the longitudinal vortices are well known for the enhancement of heat transfer in compact heat exchangers. The present investigation determines the heat transfer characteristics with secondary flow analysis in plate fin triangular ducts with delta wing vortex generators. This geometrical configuration is investigated for various angles of attack of the wing i.e. 15°, 20°, 26° and 37° and Reynolds numbers 100 and 200. The constant wall temperature boundary condition is used. The solution of the complete Navier Stokes equation and the energy equation is carried out using the staggered grid arrangement. The performance of the combination of triangular secondary fins and delta wing with stamping on slant surfaces has also been studied. Copyright © 2009 John Wiley & Sons, Ltd.     

An elastic wave scattering problem relating to the rapid movement of a fracture in a plate: Part II — Numerical results

In Part I of this two part paper, we developed analytical expressions for the crack face displacements due to an applied point traction as well as a moving point source of dilatation. In this sequel to Part I, we present numerical results for the crack face displacements in the form of displacement-time records at fixed locations on the crack face. For the stationary point traction problem, the results are more or less in keeping with the predictions made in Part I, with the Rayleigh pulse giving a large contribution for an applied step load.In the case of the moving point microfracture with a step time dependence, in addition to the diffracted compressional, shear and Rayleigh arrivals there is observed the evolution of a new pulse whose amplitude and position on the time record shifts changes if the calculations are done for a different crack speed. Results are also presented for a microfracture with an oscillatory time dependence. Once again, the first arrival of the surface pulse appears to be the most prominent arrival on the record. Further explorations of the parameters and source functions would be required before comparisons with experimental data can be made.     

Finite-dimensional quantum mechanics of a particle

This paper analyzes the possible implications of interpreting the finitedimensional representations of canonically conjugate quantum mechanical position, and momentum operators of a particle consistent with Weyl's form of Heisenberg's commutation relation as the actual position, and momentum operators of the particle when it is confined to move within a finite spatial domain, and regarding the application of current quantum mechanical formalism based on Heisenberg's relation to such a situation as an asymptotic approximation. In the resulting quantum mechanical formalism the discrete and finite position and momentum spectra of a particle depend on its rest mass and the spatial domain of confinement. Such a finite-dimensional quantum mechanics may be very suitable for describing the physics of particles confined to move within very small regions of space.     

Solution of the differential equation (∂2∂x∂y + ax∂∂x + by∂∂y + cxy + ∂∂t) P(x,y, t) = 0 and the Bogoliubov transformation

An eigen function expansion for the solution of the Lambropolous partial differential equation is obtained by the use of a transformation similar to the Bugolubov transformation familiar in Bose gas theory. Also the technique of normal ordering of operators is employed. The orthogonality properties of such solutions are also analysed.