Chemical bonding in view of electron charge density and kinetic energy density descriptors

Stalke's dilemma, stating that different chemical interpretations are obtained when one and the same density is interpreted either by means of natural bond orbital (NBO) and subsequent natural resonance theory (NRT) application or by the quantum theory of atoms in molecules (QTAIM), is reinvestigated. It is shown that within the framework of QTAIM, the question as to whether for a given molecule two atoms are bonded or not is only meaningful in the context of a well‐defined reference geometry. The localized‐orbital‐locator (LOL) is applied to map out patterns in covalent bonding interaction, and produces results that are consistent for a variety of reference geometries. Furthermore, LOL interpretations are in accord with NBO/NRT, and assist in an interpretation in terms of covalent bonding. © 2008 Wiley Periodicals, Inc.J Comput Chem, 2009.     

Global existence and exponential stability for a contact problem between two thermoelastic beams

In this paper we analyze a dynamic unilateral contact problem between two thermoelastic beams. We establish the existence of a weak global-in-time solution, by a penalization method. Moreover, we study the asymptotic behavior of such a solution proving that the energy associated to the system decays exponentially to zero, as time goes to infinity.     

Low‐temperature sol–gel transformation of methyl silicon precursors to silica‐based hybrid materials

Six new methyl silicon (IV) precursors of the type [MeSi{ON?C(R)Ar}₃] [when R = Me, Ar = 2‐C₅H₄N ( 1 ), 2‐C₄H₃O ( 2 ) or 2‐C₄H₃S ( 3 ); and when R = H, Ar = 2‐C₅H₄N ( 4 ), 2‐C₄H₃O ( 5 ) or 2‐C₄H₃S ( 6 )] were prepared and structurally characterized by various spectroscopic techniques. Molecular weight measurements and FAB (Fast Atomic Bombardment) mass spectral studies indicated their monomeric nature. ¹H and ¹³C{¹H} NMR spectral studies suggested the oximate ligands to be monodentate in solution, which was confirmed by ²⁹Si{¹H} NMR signals in the region expected for tetra‐coordinated methylsilicon (IV) derivatives. Thermogravimetric analysis of 1 revealed the complex to be thermally labile, decomposing to a hybrid material of definite composition. Two representative compounds ( 2 and 4 ) were studied as single source molecular precursor for low‐temperature transformation to silica‐based hybrid materials using sol–gel technique. Formation of homogenous methyl‐bonded silica materials (MeSiO_3/2) at low sintering temperature was observed. The thermogravimetric analysis of the methylsilica material indicated that silicon‐methyl bond is thermally stable up to a temperature of 400 °C. Reaction of 2 and Al(OPrⁱ)₃ in equimolar ratio in anhydrous toluene yielded a brown‐colored viscous liquid of the composition [MeSi{ON?C(CH₃)C₄H₃O}₃.Al(OPrⁱ)₃]. Spectroscopic techniques ¹H, ¹³C{¹H}, ²⁷Al{¹H} and ²⁹Si{¹H} NMR spectra of the viscous product indicated the presence of tetracoordination around both silicon and aluminum atoms. On hydrolysis it yielded methylated aluminosilicate material with high specific surface area (464 m²/g). Scanning electron micrography confirmed a regular porous structure with porosity in the nanometric range. Copyright © 2008 John Wiley & Sons, Ltd.     

SET‐LRP of acrylates in the presence of radical inhibitors

The Cu(0)/Me₆‐TREN‐catalyzed single‐electron transfer mediated living radical polymerization (SET‐LRP) of methyl acrylate in the presence of the classic 4‐methoxyphenol free radical inhibitor was investigated. Kinetic experiments, combined with ¹H NMR, and MALDI‐TOF MS analysis of the resulting polyacrylates demonstrated that SET‐LRP is a robust synthetic method that does not require the purification of the monomers to remove the radical inhibitor. It is anticipated that these results will contribute to the expansion of technological and fundamental applications of SET‐LRP since it allows the synthesis of polymers with a structural perfection that previously was not accessible by any other method, starting from unpurified monomers, solvents, initiators, and ligands. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 3174–3181, 2008     

Anchorage strength models for end-debonding predictions in RC beams strengthened with FRP composites

The increase in the flexural capacity of RC beams obtained by externally bonding FRP composites to their tension side is often limited by the premature and brittle debonding of the external reinforcement. An in-depth understanding of this complex failure mechanism, however, has not yet been achieved. With specific regard to end-debonding failure modes, extensive experimental observations reported in the literature highlight the important distinction, often neglected in strength models proposed by researchers, between the peel-off and rip-off end-debonding types of failure. The peel-off failure is generally characterized by a failure plane located within the first few millimetres of the concrete cover, whilst the rip-off failure penetrates deeper into the concrete cover and propagates along the tensile steel reinforcement. A new rip-off strength model is described in this paper. The model proposed is based on the Chen and Teng peel-off model and relies upon additional theoretical considerations. The influence of the amount of the internal tensile steel reinforcement and the effective anchorage length of FRP are considered and discussed. The validity of the new model is analyzed further through comparisons with test results, findings of a numerical investigation, and a parametric study. The new rip-off strength model is assessed against a database comprising results from 62 beams tested by various researchers and is shown to yield less conservative results. Russian translation published in Mekhanika Kompozitnykh Materialov, Vol. 44, No. 3, pp. 373–388, May–June, 2008.     

Straightness Measurement Using Laser Diode and CCD Camera

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Synthesis of unsymmetrical saturated or diacetylenic cationic bolaamphiphiles

This work presents the synthesis of novel unsymmetrical bolaamphiphiles bearing a sugar residue and a cationic glycine betaine moiety connected to both ends of a C₂₂ or C₃₂ oligomethylene bridging chain possessing or not a diacetylenic unit. Preliminary transmission electron microscopy (TEM) studies revealed the polymorphism of these bola lipids with regard to their self-assembled morphologies in water depending on the presence or not of the diacetylenic functionality and on alkyl chain length.     

Effect of argon on the multibubble sonoluminescence of cerium,terbium, and dysprosium trichlorides

The ultrasonic (20 kHz) multibubble sonoluminescence spectra of aqueous air- or argon-saturated solutions of CeCl₃, TbCl₃, and DyCl₃ were obtained. Saturation with argon leads to the intensity redistribution in the spectrum of the continuum with an increase in its short-wavelength part and increases the intensity of the characteristic emission of Ce³⁺ and Tb³⁺ due to the enhancement of the sonophotoluminescence intensity, i.e., the re-emission of the absorbed part of the continuum by these ions. The Ce³⁺, Tb³⁺, and Dy³⁺ ions quench the OH* emission at 310 nm with a qualitative correlation between the degree of quenching and the standard redox potentials of the pairs Ln^IV/Ln^III. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1797–1802, September, 2008.     

Gouy phase compensation in quasi-phase matching

In any focussed nonlinear interaction the focus induced phase shift, known as the Gouy phase shift, provides an imperfection in phase matching for any linearly invariant material. However, using an appropriately designed quasi-phase matched structure it is theoretically possible to compensate for the deleterious effects of the Gouy phase shift, allowing a symmetric frequency response and tighter optimal focussing than in a uniform material.