Novel halogenated cyclopentasilylene-2,4-dienes via DFT

In view of immense importance of silylenes and the fact that their properties undergo significant changes on substitution with halogens, here, we have used B3LYP/6-311++G** level of theory to access the effects of 1–4 halogens (X = F, Cl, Br, and I) on four unprecedented sets of cyclopentasilylene-2,4-dienes; with the following formulas: SiC₄H₃X ( 1 _X ), SiC₄H₂X₂ ( 2 _X ), SiC₄HX₃ ( 3 _X ), and SiC₄X₄ ( 4 _X ). In going down from F to I, the singlet (s)-triplet (t) energy gap (ΔE_s-t, a possible indication of stability), and band gap (ΔE_H-L) decrease while nucleophilicity (N), chemical potential (μ), and proton affinity (PA) increase. The overall order of N, μ, and PA for each X is 2 _X > 1 _X > 3 _X > 4 _X . Precedence of 2 _X over 1 _X is attributed to the symmetric cross conjugation in the former. The highest and lowest N are shown by 2 _I and 4 _F . The trend of divalent angle () for each X is 4 _X > 1 _X > 3 _X > 2 _X . The results show that in going from electron withdrawing groups (EWGs) to electron donating groups (EDGs), the ΔE_s-t and ΔE_H-L decrease while N, μ, and PA increase. Also, rather high N of our scrutinized silylenes may suggest new promising ligands in organometallic chemistry.     

Convective Heat Transfer past Small Cylindrical Bodies

Convective heat transfer from an array of small, cylindrical bodies of arbitrary shape in an unbounded, two-dimensional domain is a singular perturbation problem involving an infinite logarithmic expansion in the small parameter ε, representing the order of magnitude of the size of the bodies. Using the method of matched asymptotic expansions, we formulate a hybrid asymptotic-numerical method to solve for the dimensionless, steady-state temperature. We assume that the velocity field of the fluid surrounding the bodies is arbitrary but known. From our asymptotic solution for an arbitrary velocity field, we present the results for two special cases: a uniform flow field and a simple shear flow field. We demonstrate the asymptotic results of the hybrid method through a number of examples and, in a particular case, we compare these results to an exact analytical solution.     

On the Representation of Band-Dominant Functions on the Sphere Using Finitely Many Bits

A band-dominant function on the Euclidean sphere embedded in R ^q+1 is the restriction to this sphere of an entire function of q+1 complex variables having a finite exponential type in each of its variables. We develop a method to represent such a function using finitely many bits, using the values of the function at scattered sites on the sphere. The number of bits required in our representation is asymptotically the same as the metric entropy of the class of such functions with respect to any of the L ^p norms on the sphere.     

Studies on Rare-Earth/Iron and Actinide/Iron Multilayers

Hyperfine Interactions - Multilayers of Ce/Fe and U/Fe were fabricated by sputtering and studied by X-ray diffraction and reflectivity, Mössbauer spectroscopy and polarised neutron...     

Rank-one completions of partial matrices and completely rank-nonincreasing linear functionals

We obtain necessary and sufficient conditions for the existence and the uniqueness of rank-one completions of a partial matrix, and we verify a conjecture of Hadwin and Larson concerning the nature of completely rank-nonincreasing linear functionals defined on pattern subspaces.

     

Complex polymer architectures through dimethoxymethyl 1,1‐diphenylethylene derivatives

The reactions of polystyryllithium and potassium on dimethoxymethyl 1,1‐diphenylethylene derivatives were studied in different solvents. In a polar medium, A₃ and A₆ star types were formed according to the stoichiometry, whereas in a nonpolar medium, hyperbranched structures were synthesized. Extensions of an already proposed mechanism in polar and nonpolar media were examined. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3329–3335, 2003     

Sobolev bounds on functions with scattered zeros, with applications to radial basis function surface fitting

In this paper we discuss Sobolev bounds on functions that vanish at scattered points in a bounded, Lipschitz domain that satisfies a uniform interior cone condition. The Sobolev spaces involved may have fractional as well as integer order. We then apply these results to obtain estimates for continuous and discrete least squares surface fits via radial basis functions (RBFs). These estimates include situations in which the target function does not belong to the native space of the RBF.

     

Contour lines of the optical functions for solids

The well-known equations for the optical functions of reflectance, transmittance and phase changes on reflection and transmission for a solid material have been rearranged into the form of simple geometric figures in the u, v (n, k) plane. The curves for F_p show a singularity on the n-axis.