A new microwave dielectric method for studying photoinitiated chain radical polymerization processes

Measurements of both real and imaginary parts of the dielectric constant at a fixed microwave frequency have been performed on n-butyl acrylate/poly(n-butyl acrylate) mixtures. The dielectric constant of the mixtures has been compared with that of neat n-butyl acrylate during UV photoinitiated polymerization. The values of the imaginary part of the dielectric constant thus obtained have allowed determination of the instantaneous monomer concentration and verified the kinetic equation for the photoinitiated polymerization process. The limits of validity of the method as well as its capability of providing detailed kinetic information are also discussed.     

Negative ion chemical ionization mass spectra of (η6-arene)Cr(CO)3

The negative ion chemical ionization mass spectra, with ammonia and methane as reagent gases, of the (η⁶-arene)Cr(CO)₃ complexes, where the arene is C₆H₅COCH₃, C₆H₅COC₂H₅, C₆H₅COC₃H₇, C₆H₅COC(CH₃)₃, 2-CH₃C₆H₄COC₃H₇, C₆H₅COOCH₃, C₆H₅CH₃, 1,3,5-(CH₃)₃C₆H₃ and C₆H₅CH₂COC₂H₅, are reported. Similar behaviour is observed with the two reagent gases, but ammonia shows a much higher abundance for the ions produced by reactions of [NH₂]^? with sample molecules. The compounds containing the C₆H₅CO group display an abundant [M]^{? ˙}, whereas the other compounds exhibit [M? H]^? as base peak, produced by ion/molecule reactions. A comparison of the negative ion chemical ionization mass spectra of the (η⁶-arene)Cr(CO)₃ complexes with those of the corresponding ligands shows the strong electron withdrawing power of the Cr(CO)₃ group in the gas phase.     

Reaction of singlet oxygen with some benzylic sulfides

Product distribution, total quenching rate (k_T), and rate of chemical reaction (k_r) with singlet oxygen have been determined for some alkyl, benzyl, α-methylbenzyl, and cumyl sulfides. Their contributions depend on the steric hindering around the sulfur atom. In protic solvents, the sulfoxide is the main product via a hydrogen-bonded persulfoxide. In apolar solvents, intramolecular α-H abstraction leads to oxidative C-S bond cleavage, with varying efficiency. The behavior of sulfides is compared to that of alkenes and amines.     

Crystal,molecular and electronic structure of 1,1-diaryl-2-halogenoethylenes

On the basis of semiempirical calculations, the conformation of the isolated molecule of 2-bromo-1,1-diphenylprop-1-ene corresponding to the minimum of total energy was determined. Assuming some information on the localization of the molecules in the crystal, also the conformation in a theoretical crystal was studied. The results have been compared with the crystal structure of 2-bromo-1,1-diphenylprop-1-ene, as obtained by X-ray diffraction. From the comparison a slight displacement of the C2 atom was suggested.

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Zusammenfassung Die dem Minimum der Gesamtenergie entsprechende Konformation des isolierten Moleküls von 2-Brom-1,1-diphenylprop-1-en wurde durch halb-empirische Methoden bestimmt. Gewisse Ergebnisse über die Anordnung der Moleküle im Kristall machten es möglich, die Konformation in einem theoretischen Kristall zu untersuchen. Nach Vergleich der Resultate mit der durch Röntgen-Analyse bestimmten Kristallstruktur des 2-Brom-1,1-diphenylprop-1-en wurde eine kleine Verschiebung des C2-Atoms vorgeschlagen.

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Résumé Par le moyen de calculs semiempiriques on a déterminé la conformation de la molécule isolée de 2-bromo-1, 1-diphénilprop-1-ène, correspondant au minimum d'énergie totale. On a aussi étudié la conformation dans le cristal théorique en se basant sur des informations concernant la localisation des molécules dans le cristal. On a comparé ces résultats avec ceux que nous avons obtenus par la détermination de la structure cristalline du 2-bromo-1, 1-diphénilprop-1-ène avec la diffraction des rayons X: cette comparaison nous a porté à déplacer un petit peu l'atome C 2.

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This work was supported by a grant from the Italian Consiglio Nazionale delle Ricerche.     

The bent RC  N linkage: An AB initio study of NH2CN,NF2CN and PF2CN

The ab initio energies, nuclear and electron repulsions and charge distributions have been calculated using moderately large basis sets as a function of the RC  N angle (R  NH₂, NF₂ or PF₂). The optimum RC  N angles were calculated to be 178.9°, 176.6°, and 175° for NH₂CN, NF₂CN, and PF₂CN, respectively. A rationalization of the differing bends is presented in terms of nuclear-nuclear and electron-electron repulsions.     

A damage constitutive model for sliding friction coupled to wear

Several new constitutive models are formulated for the planar interface of a soft body sliding on a rigid soil, describing stick-slip phenomena due to friction, and wear due to abrasion. Attention is focused on damage at the interface, by neglecting any interaction with damage of body and any propagation of damage inside the body. Models are formulated in the general framework of the Thermodynamics of the irreversible processes and account for suitable defined internal variables of phenomenological type, namely gap, isotropic friction hardening and wear. The main feature of the new presented models is that the formulation of the wear process at the interface is obtained in the contest of Damage Mechanics, and it is based on the formal analogy between abrasion of a soft body and ductile damage of an elastic-plastic material. By following this approach, a scalar wear field, an effective stress and appropriate state and dissipation potentials are defined, able to describe a tangential isotropic wear process due to stick-slip and to hardening mechanism. Both cases of linear and nonlinear friction hardening are formulated; moreover, wearable and no-wearable bodies are considered. Numerical results relevant to one-dimensional problems are illustrated for monotonic, forward-backward and cyclic displacement time-histories, showing evolution for stress, gap and wear. Results furnished by different models are compared and discussed.     

On continuation of inviscid vortex patches

This investigation concerns solutions of the steady-state Euler equations in two dimensions featuring finite area regions with constant vorticity embedded in a potential flow. Using elementary methods of the functional analysis we derive precise conditions under which such solutions can be uniquely continued with respect to their parameters, valid also in the presence of the Kutta condition concerning a fixed separation point. Our approach is based on the Implicit Function Theorem and perturbation equations derived using shape-differentiation methods. These theoretical results are illustrated with careful numerical computations carried out using the Steklov–Poincaré method which show the existence of a global manifold of solutions connecting the point vortex and the Prandtl–Batchelor solution, each of which satisfies the Kutta condition.     

New search for processes violating the Pauli exclusion principle in sodium and in iodine

In this paper a new search for non-Paulian nuclear processes, i.e. processes normally forbidden by the Pauli Exclusion Principle (PEP), is presented. It has been carried out at the Gran Sasso National Laboratory of the INFN by means of the highly radiopure DAMA/LIBRA set-up (sensitive mass of about 250 kg highly radiopure NaI(Tl)). In particular, a new improved upper limit for the spontaneous non-Paulian emission rate of protons with energy E _p ≥ 10 MeV in ²³Na and ¹²⁷I has been obtained: 1.63 × 10⁻³³ s⁻¹ (90% C.L.). The corresponding limit on the relative strength (δ ²) for the searched non-Paulian transition is δ ²≲(3–4)×10⁻⁵⁵ (90% C.L.). Moreover, PEP-violating electron transitions in iodine atoms have also been investigated. Lifetimes shorter than 4.7×10³⁰ s are excluded at 90% C.L.; this allows us to derive the limit δ _e ²<1.28×10⁻⁴⁷ (90% C.L.). This latter limit can also be related to a possible finite size of the electron in composite models of quarks and leptons providing superficial violation of the PEP; the obtained upper limit on the electron size is r ₀<5.7×10⁻¹⁸ cm (energy scale of E≳3.5 TeV).