Gas‐Phase Infrared Spectroscopy of Substituted Cyanobutadiynes: Roles of the Bromine Atom and Methyl Group as Substituents

The IR spectra of 5‐bromo‐2,4‐pentadiynenitrile (Br?C≡C?C≡C?CN) and 2,4‐hexadiynenitrile (CH₃?C≡C?C≡C?CN), a compound of interstellar interest, have been recorded within the 4000–500 cm^?1 spectral region and calculated by means of high‐level ab initio and density functional calculations. Although the calculated structures of both compounds are rather similar, there are very subtle differences, mainly in the strength of the C≡C bond not directly bound to the substituent. These subtle bonding differences are reflected in small, but not negligible, differences in the electron density at the corresponding bond critical points, and, more importantly, are reflected in the IR spectra. Indeed, the IR spectrum for the bromine derivative presents two well‐differentiated strong bands around 2250 cm^?1, whereas for the methyl derivative both absorptions coalesce in a single band. These bands correspond in both cases to the coupling between C≡C and C≡N stretching displacements. A third, very weak, band also associated with C≡C and C≡N coupled stretches is observed for the bromine derivative, but not for the methyl one, owing to its extremely low intensity.     

Dynamic light scattering study of the ultrasonication of P(VDF-TrFE): A new model

The purpose of this paper is to understand the mechanisms occurring during the ultrasonication of the copolymer poly(vinylidenedifluoride-trifluoroethylene). In these experimental conditions, the polymer adopts a core–shell structure and its hydrodynamic diameter is measured by dynamic light scattering. The results show that, without covalent bonds breakage, the hydrodynamic diameter decreases with ultrasonication time and a smaller size population appears. This evolution is reversible in a matter of days. A new two-step mechanism is proposed to describe this phenomenon: first the erosion of a core–shell structure and second the contraction of the core. Beyond shedding a new light on the phenomena occurring during the sonication of polymers used in nanocomposites elaboration, this work also strongly questions the traditional techniques used to study the degradation of polymers, which use the hydrodynamic diameter measurement to determine the molecular weight.     

Structural,electrical, magnetic and NMR study of the NaxCrxTi1−xS2 system

Two phases are characterized in the Na_xCr_xTi_1?xS₂. The first one spans the composition range 0.34 < x < 0.71, the alkali-metal ions occupying trigonal prismatic sites. The second one which is isotypic with NaCrS₂ is found in the range 0.87 < x ? 1, the alkali-metal ions being this time in octahedral sites. Electrical measurements performed by the complex impedance method show that the conductivity is thermally activated. Magnetic and NMR experiments indicate the existence of localized magnetic moments on the chromium ions. These moments induce a shift of the NMR line and produce the most important contribution to the relaxation. The variation of the Curie temperature seems to indicate a continuous weakening of the ferromagnetic coupling between chromium ions of the same layer as the number of chromium ions decreases. An antiferromagnetic coupling then becomes preponderant.     

Sur les propriétés électriques et magnétiques des phases MxZrS2 (M = Fe,Co, Ni)

The M_xZrS₂ systems with M = Fe, Co, Ni have been investigated: nonstoichiometric phases are observed with M in the tetrahedral sites between ZrS₂ layers. Electric measurements characterize a semiconducting behaviour and suggest the occurrence of trigonal zirconium + III clusters. Magnetic measurements seem to confirm also MM bond formation.     

Poisson's ratio and the densification of glass under high pressure

Because of a relatively low atomic packing density, (Cg) glasses experience significant densification under high hydrostatic pressure. Poisson's ratio (nu) is correlated to Cg and typically varies from 0.15 for glasses with low Cg such as amorphous silica to 0.38 for close-packed atomic networks such as in bulk metallic glasses. Pressure experiments were conducted up to 25 GPa at 293 K on silica, soda-lime-silica, chalcogenide, and bulk metallic glasses. We show from these high-pressure data that there is a direct correlation between nu and the maximum post-decompression density change.     

Optical electron transfer through 2,7-diethynylfluorene spacers in mixed-valent complexes containing electron-rich "(η2-dppe)(η5-C5Me5)Fe" endgroups

We report in this communication the study of the intramolecular electron transfer through a 2,7-diethynylfluorenyl spacer in the Fe(II)/Fe(III) mixed-valent (MV) complex [(η(2)-dppe)(η(5)-C(5)Me(5))FeC≡C(2,7-C(21)H(24))C≡CFe(η(5)-C(5)Me(5))(η(2)-dppe)][PF(6)] (1[PF(6)]). The complex is generated in situ by comproportionation from its homovalent dinuclear Fe(II) and Fe(III) parents (1 and 1[PF(6)](2)). It is shown that electronic delocalization is much more effective through a 2,7-fluorenyl than through a 4,4'-biphenyl bridging unit.     

Charge density wave transport in (TaSe4)2I

We report non linear transport properties below the metal-insulat transition temperature T_° = 263 K in the halogened metal transition tetrachalcogenide (TaSe₄)₂I. These non linear properties are similar to those of NbSe₃ and TaS₃ and indicate that (TaSe₄)₂I is a new compound exhibiting charge density wave transport.     

Phase transitions in NbSe3

We describe the physical properties of the transition metal trichalcogenide NbSe₃ including electrical resistivity, magnetic susceptibility, and heat capacity. NbSe₃ undergoes phase transitions at 145 and 59 K. The effect of pressure on these transitions is also reported. We try to explain the physical properties of NbSe₃ in terms of the formation of charge density waves.     

An application of Curie’s principle to elastoplastic dynamics

This paper deals with the stability and the dynamics of a harmonically excited elastic–perfectly plastic unsymmetrical oscillator. Stability of the periodic orbits is analytically investigated with a perturbation approach. The occurrence of ratcheting effect is discussed for this system, and is related to the loss of symmetry of the periodic orbit in the phase space. Curie’s principle of symmetry is numerically verified for the symmetrical system with positive damping. Therefore, the observation of ratcheting phenomenon is necessarily associated to a breaking of symmetry in the constitutive behaviour, or in the forcing term. However, the generalized version of Curie’s principle has to be considered when a negative damping is introduced.