On the structure of CH5+; A study of hydron transfer reactions from CH4H+ and CD4H+ tandem-ICR

Relative rates of proton and deuteron transfer from CH₄D⁺ and CD₄H⁺ to a number of molecules were examined in a tandem-ion cyclotron resonance instrument. The results were in conflict with the recent work of Sefcik et al. and support a randomized model.     

Dirac's aether in relativistic quantum mechanics

The introduction by Dirac of a new aether model based on a stochastic covariant distribution of subquantum motions (corresponding to a vacuum state alive with fluctuations and randomness) is discussed with respect to the present experimental and theoretical discussion of nonlocality in EPR situations. It is shown (1) that one can deduce the de Broglie waves as real collective Markov processes on the top of Dirac's aether; (2) that the quantum potential associated with this aether's modification, by the presence of EPR photon pairs, yields a relativistic causal action at a distance which interprets the superluminal correlations recently established by Aspect et al.; (3) that the existence of the Einstein-de Broglie photon model (deduced from Dirac's aether) implies experimental predictions which conflict with the Copenhagen interpretation in certain specific testable interference experiments.     

The Legacy of Raimond Castaing

 In April 1998 Raimond Castaing left the world of electrons, of ions and others particles, his wife and his family, his numerous students, for the world of stars. Raimond Castaing (Fig. 1) had a very strong personality. No one will forget their first meeting with him and all his students remember how brilliant he was as a teacher. A lot of anecdotes about his famous hot temper are still circulating among his friends and his former students. But in this paper, we would like to evoke Castaing’s memory through his achievements in Instrumental Physics, from the time of his doctoral thesis to later developments with his students, which were all centred on the imaging of the microstructures of materials and their quantitative chemical analysis.     

Etude des propriétés cristallographiques,diélectriques et d'optique non linéaire de quelques nouvelles phases de composition BaxLi5−2xNb5(1−y)Ta5yO15 et de structure bronzes oxygénés de tungstène quadratiques

Two series of phases with tetragonal bronze-like structure and composition Ba_xLi_5?2xT₅O₁₅ (T = Nb, Ta) have been isolated in the systems BaNb₂O₆LiNbO₃ and BaTa₂O₆LiTaO₃. All these phases show ferroelectric-paraelectric transitions. The Curie temperature increases with the lithium content. The value of T_C for Ba_2.03Li_0.94Nb₅O₁₅ is the highest ever observed for this type of structure: the obtained phases are potentially good materials for the harmonic generation of the 0.53-μm radiation. The optical yield of the niobate Ba_2.14Li_0.71Nb₅O₁₅ is about 2.5 times that of Ba₂NaNb₅O₁₅ and 250 times that of the K.D.P. The crystallographic and dielectric data of the system Ba_2.14Li_0.71Nb₅O₁₅Ba_2.14Li_0.71Ta₅O₁₅ characterize three domains, which are respectively antiferroelectric, ferroelectric, and paraelectric. The Curie temperature and the optical yield decrease with increasing tantalum content.     

Analyse de population dans les calculs LCAO: charges et moments atomiques

Résumé Les auteurs montrent que le moment dipolaire d'une molécule peut, avec une bonne approximation, se réduire à la somme vectorielle des moments atomiques et d'un moment de charges ponctuelles centrées sur les atomes. Les charges ainsi définies sont indépendantes du système d'axes de coordonnées.

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Population analysis by LCAO calculations: Charges and atomic moments

The authors show that the dipole moment of a molecule can be reduced to the vector sum of the atomic moments and of a moment due to point charges centred on atoms with a good accuracy. The so defined charges are independent of the coordinate system.

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Zusammenfassung Die Autoren zeigen, daß das Dipolmoment von Molekülen als Vektorsumme der Atommomente und eines Moments, das von Punktladungen an den Atomen herrührt, dargestellt werden kann. Die dabei definierten Ladungen sind unabhängig vom Koordinatensystem.

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Equipe de Recherche Associée au C.N.R.S. n 22.

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Remerciements. Ce travail a été en partie présenté au 2ème Colloque International des Chimistes Théoriciens d'expression latine (Paris, septembre 1970).Les auteurs remercient les participants à ce Colloque et en particulier Madame A. Pullman et Monsieur P. Claverie pour leurs remarques et leurs suggestions. Leur gratitude va également au Centre National de la Recherche Scientifique pour l'aide matérielle qu'il apporte à ces recherches.     

Cyclocopolymerization of dicyclic dienes and maleic anhydride to fused ring systems

The cyclocopolymerization of maleic anhydride and four 1,5- and 1,6-dienes (bicyclopentene, bicyclohexene, dicyclopentenyl ether, and dicyclohexenyl ether) and one tetraene (quartercyclopentene) is described. Soluble, low molecular weight copolymers were obtained from all five compounds. Their compositions approach 2:1 copolymer ratios. Fused ring structures are proposed as the main repeating units. Among the compounds listed, bicyclopentene copolymerized most easily and gave good conversions for monomer ratios of 2:1. Quartercyclopentene and dicyclopentyl ether, the other five-membered ring compounds, also polymerized to good-to-fair yields. However, a monomer ratio of about 4:1 was required to obtain conversions comparable to a 2:1 maleic anhydride—bicyclopentene polymerization. The six-membered systems, bicyclopentene and dicyclopentenyl ether, gave consistently low conversions, even with a 4:1 monomer ratio. The influence of the initiator system, initiator concentration, and reaction medium was studied on copolymerizations of bicyclopentene. Best results were obtained in acetic anhydride with azobisisobutyronitrile as the initiator.     

Dipolar relaxations in an epoxy-amine system

Dipolar relaxations in a reactive epoxy-amine system based on diglycidyl ether of bisphenol A with 4,4^′-diaminodiphenylsulfone were studied with the Havriliak-Negami function. The system was cured isothermally at 140 °C using simultaneous kinetic and microdielectric studies.The relaxation time was calculated from the frequency f_max of the peak of the loss factor ε^′′ versus frequency f. A linear relation exists between the logarithm of the relaxation time τ and the glass transition temperature T_g. Then, logτ follows the Di Benedetto equation revisited by Pascault and Williams allowing the prediction of the relaxation time τ during cure.The unrelaxed permittivity at high frequency ε_u, the relaxed or static permittivity ε_s and the skewness parameter β were found independent on the conversion or the curing time. The distribution parameter α decreases as curing time t increases. The difficulty of orientation of dipoles in the electric field due to vitrification is responsible of these behaviours.     

Spectrométrie de Masse—IV: Fragmentation des Dicétones—ϵ

The mass spectra of ten symmetrical ?-diketones are reported and a number of fragmentation patterns are documented by deuterium labelling experiments. The McLafferty rearrangement involving one of the carbonyl groups is not an important fragmentation pathway although such a double rearrangement is observed for long-chained ?-diketones. Special attention has been given to the ions resulting from the loss of either a molecule of water or the neutral species C₂H₄ which may involve an electron-impact induced formation of cyclobutanol-type ions analogous to the photochemical Yang's reaction.     

Oligothienylenevinylenes incorporating 3,4-ethylenedioxythiophene (EDOT) units

A new series of π-conjugated oligomers based on various combinations of thiophene and EDOT units and double bonds has been synthesized by Wittig-Horner reactions from phosphonate anions carrying EDOT or bis-EDOT units. Optical and electrochemical results evidence the crucial role of the EDOT moiety for modulating the electronic properties of the oligomers. The insertion of bis-EDOT unit in the middle of the molecule leads to a self-rigidification of the conjugated system due to non covalent S?O intramolecular interactions. The strong electron donor effect of the EDOT units explains the determining role of the relative position of the EDOT units on the localization and stabilization of the positive charges in the radical cation or dication states.     

Photodissociation of CH4+ via ion cyclotron resonance

The molecular methane ion CH₄⁺ was observed to dissociate to the methyl cation and a hydrogen atom upon irradiation with while light from a 2.5 kW xenon are lamp. The maximum photodissociation cross section was estimated as 3×10^?19 cm² at 3350 Å and a spectrum was obtained.