Potential energy surfaces for HenNe+ ions: ab initio and diatomics-in-molecule results

The potential energy surface of He2Ne+ has been reinvestigated using a combination of ab initio and diatomics-in-molecule (DIM) calculations. In contrast to the reports of two recent studies the ion is found to have an asymmetric linear He-Ne-He structure, with no barrier to formation from the separated atoms on the ground-state surface. The He-Ne+ bond lengths at the potential minimum are 1.51 and 1.81 A, and the total bonding energy is 0.717 eV. Comparing the He2Ne+ energy to that of HeNe+, the bonding energy for the second helium atom is 0.06 eV, about 10% of that of the first He atom. The saddle point between the two equivalent minima is a symmetric structure, 0.0074 eV above the potential minimum. A symmetric geometry becomes the overall potential minimum if the 2s hole on the Ne is excluded from the reference states of a multireference configuration interaction calculation. A DIM potential was created for the HenNe+ family of ions. The DIM potential is consistent with the asymmetric He2Ne+ ion serving as a core; it predicts a slightly more asymmetric geometry than the ab initio results. Additional helium atoms form five-membered rings around the bonds of the core ion to fill the first shell and then add to the ends of the cluster. The asymmetric core ion and the highly compact structure help to account for the lack of apparent shell structure in the mass spectrometry of HenNe+ clusters. Finally, we recommend that the value De=0.63+/-0.04 eV be adopted for the ground state of HeNe+.     

1,3-Dipolare Addition von 2-Benzonitrilio-2-propanid an 7-Methylthieno[2,3-c]pyridin-1,1-dioxid und Folgereaktionen

1,3-Dipolar Addition of 2-Benzonitrilio-2-propanid to 7-Methylthieno[2,3-c]pyridine 1,1-Dioxide and Subsequent Reactions The addition of dipole 2 , generated photochemically from 2,2-dimethyl-3-phenyl-2H-azirine ( 1 ), to 7-methylthieno[2,3-c]pyridine 1,1-dioxide yields the pyrroline derivative 4 as a major product and regioisomer 5 in low yield. Compound 4 can be transformed into the pyrrolidine derivative 11 by ring opening, loss of SO₂ and hydrogenation. Bromopyrroline derivative 14 gives either by dehydrohalogenation compound 18 or, by substitution, nitrile 17 or ethoxy derivative 19 . Substitution of 14 and ring opening yields methoxypyrrole derivative 20 , which gives access to the unstable hydroxypyrrole and hydroxypyrrolidine derivative 28 resp. 30 . The vinylsulfone 18 is the starting material for addition-ring-cleavage reactions. Oxidation of pyrroline derivative 4 gives epoxy-substituted N-oxide 39 and di-N-oxide 40 ; and oxidative transformation of pyrrolidine derivative 11 yields the (hydroxymethyl)pyridylpyrrolidine derivative 45 .     

Stereoselective Syntheses of Tetrahydroesterastin-β -Lactam Analogues

A total synthesis of the optically active tetrahydroesterastin β -lactam analogue 2 using Miller's hydroxamate approach is described (Scheme 2). Significant modification of published procedures has resulted in a short and facile stereospecific preparation of the N-[(benzyloxycarbonyl)methyl]-β -lactam 17 starting from the readily available D -serine. This material served as intermediate for the preparation of a variety of N-[(benzyloxycarbonyl)methyl]tetrahydroesterastin β-lactam analogues (Scheme 5).     

Etude quantitative de la distinction entre une liaison de covalence et une liaison de coordination: les molecules de borazane et d'aminoborane

Résumé On propose un exemple quantitatif de la distinction entre une liaison de covalence et une liaison de coordination; cette différenciation, fondée sur les propriétés de la molécule une fois formée, semble très nette pour les énergies de liaison, les populations de recouvrement et les charges des groupes; en particulier, un critère récent, proposé par deux des auteurs, est remarquablement vérifié. Enfin, on essaie de préciser la signification des symboles chimiques traditionnels.

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Quantitative studies of the difference between a covalence and a coordination bond: The molecules of amine-borane and aminoborane

An illustration of the distinction between these two types of chemical bonds is proposed, which is based on the properties of the molecule once built. Bond energies, overlap populations and group charges vary considerably from one compound to the other; more, a recent criterion given by two of the authors seems to be particularly suitable for describing the character of the bond. Lastly, one tries to give an explicit signification to the usual chemical symbols.

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Zusammenfassung Es wird ein quantitatives Beispiel der Unterscheidung zwischen einer kovalenten und einer koordinativen Bindung angegeben, die auf den Eigenschaften des vorliegenden Moleküls beruht. Sie erscheint sehr günstig für die Bindungsenergien, die Überlagerungspopulationen und die Gruppenladungen. Insbesondere wird ein Kriterium, das kürzlich von zwei der Autoren angegeben wurde, gut verifiziert. Schließlich wird versucht, die üblichen chemischen Symbole zu präzisieren.

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Les auteurs tiennent à remercier très vivement M. M. Berthier et Millié d'avoir mis à leur disposition le programme de localisation indispensable à ce travail, ainsi que Mademoiselle Le Guen et le C.I.R.C.E. pour la réalisation des calculs sur l'ordinateur IBM 360-75.     

Main chemical engineering parameters affecting radical polymerization processes in heterogeneous media

The main parameters which may affect both reactor performance and polymerization processes in heterogeneous media are described. Viscosity and its influence on heat and mass transfer, residence time distribution in tubular reactor, as well as, influence of agitation on coagulum formation and of monomer feed rate on polymerization rate in semi-batch processes are examined.     

Experimental study of oblique circular cylindrical apertures in plates

Ten steel plates weakened by the penetration of an oblique circular cylindrical aperture have been tested. The generator of the aperture makes 0-, 15-, 30- and 45-deg angles with the normal to the plate surface. In the case of the first seven models, the tractions were applied in the direction normal and parallel to the plane of symmetry. The strain distributions around the aperture are presented in nondimensional forms along three generators 45 deg apart. The last three models, with large aperture diameter, were tested to investigate the effect of thickness-to-diameter ratio for the three angles of skewness. The experimental results are compared with the theoretical predictions. It is noted that, for most of the plates, there was a fairly good agreement for the stress distribution throughout the thickness. The results of the experiments for uniaxial state of stress have been superimposed in order to obtain the response for various biaxial conditions.     

Addition de la proline à quelques alcènes et alcynes électrophiles

Addition of proline in acetic anhydride to propiolic and pbenylpropiolic ester gave rise to two isomeric pyrroles 5 and 6 . Addition under the same conditions, to electrophilic alkenes pY-PhCH = C(X) (CN) led to a pyrroline-2 8 which eliminated HCN and produced pyrrole 9 . Addition of proline to fumarodinitrile is unusual, the reaction led to a new α-amino acid 10 and compound 11 . The structure of this product 11 was confirmed by X-ray measurements.     

Maxima and minima of the displacement components for the Lamb modes

This paper revisits the vanishing of the transverse component of the particle displacement vector in free surfaces of an isotropic homogeneous plate, for both symmetric and antisymmetric Lamb waves. Drawing on well-known analytical expressions from Viktorov's book [(1967) Rayleigh and Lamb Waves: Physical Theory Applications, Chap. II, pp. 67-121], two distinct frequency-thickness product expressions, in cases where this vanishing occurs, are derived: one for the symmetric modes and another for the antisymmetric modes. At these frequency-thickness products, phase and group velocities have appreciable values which are discussed herein. It appears that these velocities depend on the transverse bulk wave velocity only. This is the specific condition of the Lame? modes. Moreover, theoretical and experimental investigations of displacements in the surface of a plate in air have been carried out. The theoretical part shows that the normal and transverse displacements have, respectively, a local maximum and a local minimum in the vicinity of these frequency-thickness products. The experimental part corroborates the presence of the local maximum of the S(0) Lamb mode for various materials.     

Bottom-up segmentation of image sequences for coding

A bottom-up segmentation method is presented as a first step of object based coding. An initial partition is created based on connected filters. The iterative fusion algorithm merges the most similar regions until the target is reached. As the regions become bigger, more complex criterion, like similarity of texture or of motion are used. The algorithm offers a good balance between time stability and the ability to cope with the apparition of new regions.