Fonctions aléatoires de deux variables presque surement a echantillons continus sur un domaine rectangulaire borne

Sans résumé     

Extension of a simplified method for molecular correlation energy calculations to molecules containing third row atoms. I. Methodological developments

An extension of a simplified method for molecular correlation energy calculations to molecules containing third row atoms is presented. In addition to the use of pseudo-potentials in the calculations, the consequences of this extension on the different components of the energy partition which is the basic idea of the method, is analysed. Particular emphasis is placed on the specific role played by the 3d orbitals in each of the energy components. First, at the zeroth order, the energy is found to be very sensitive to the optimization of the 3d polarization functions. Secondly, the internal correlation energy, calculated by CI, requires the optimization of distinct 3d correlation orbitals to describe adequately the strong near-degeneracy effects that occur within the valence space. Finally it is shown that the 3d orbitals contribute partially to the non-internal correlation energy and that, the atoms-in-molecule structures corresponding typically to all-external contributions are negligible. The concept of error energy is introduced in place of the non-internal correlation energy: it includes the relativistic contributions within the semi-empirical tables. Such tables are presented for second row atoms and for the chlorine atom. From these tables, predicted values for some atomic term energies, experimentally undetermined, are derived. The methodological tests are limited here to the chlorine atom which is chosen for further applications in the next paper of this series. The conclusions concerning the applicability of the method to third row atoms are however quite general.Boursier I.R.S.I.A     

Gas-phase thermolysis of sulfur compounds. Part VIII. Chloromethyl allyl,cyanomethyl allyl, 1-cyanoethyl allyl and neopentyl allyl sulfides

The pyrolyses of four alkyl allyl sulfides with substituents on the α? C atom of the alkyl moiety have been studied in a stirred-flow system over the temperature range 340-400°C and pressures between 2 and 12 torr. The only products formed are propene and thioaldehydes. The reactions showed first-order kinetics with the rate coefficients following the Arrhenius equations: Chloromethyl allyl sulfide: Cyanomethyl allyl sulfide: 1-cyanoethyl allyl sulfide: Neopentyl allyl sulfide: The effects of these and other substituents on the reactivity is discussed in relation with the stabilization of a polar six-centered transition state. The results support a non-concerted mechanism where the 1–5 α? H atom shift is assisted by its acidic character.     

Structure de la Nor-Mycosporine Glutamine,nouvelle substance isolee de Pyronema omphalodes (Bull ex Fr.) fuckel.

Nor-Mycosporin Glutamin, a new unstable compound isolated from sporulating cultures of $\text{Pyronema omphalodes}$, has the structure (I).     

Relative influence of two small parameters in non uniformly elliptic homogenization problems

We study three elliptic problems depending on two small parameters (? = homogenization parameter and δ = perturbation parameter which causes non uniform ellipticity). In each case, the homogenized operator corresponding to the second order operator is independent of the way (?, δ) → (0, 0), but the convergence results and the limit solution do depend on the relative size of ? and δ; the relevant parameter is δ?^?2.     

Sur le chlorure de formyle

Rèsumè Les auteurs n'ont pu mettre en évidence la bande d'absorption infrarouge du groupement CO vers 1800 cm^–1 relative au chlorure de formyle hypothétique.

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Summary The authors have not been able to establish the infrared absorption band of the CO group in the neighborhood of 1800 cm^–1 relative to the hypothetical formyl chloride.

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Zusammenfassung Die der Carbonylgruppe im hypothetischen Formylchlorid zugehörige Absorptionsbande bei 1800 cm^–1 ließ sich nicht nachweisen.

     

Hétérocycles contenant du phosphore. XXII—Etude par RMP de dérivés de l'oxazaphospholane-1,3,2: II—Analyse des spectres de composés monosubstitués en 5 ou disubstitués en 4 et 5.

The influence of various factors (temperature, nature and concentration of solvent) or the utilisation of various physical methods (tickling or INDOR experiments, for example) are employed to analyse the PMR spectra of some 5-monosubstituted or 4,5-disubstituted 1,3,2-oxazaphospholane derivatives.