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.     

Synthesis,characterization, and crystal structure of a new truly one-dimensional compound: PV2S10

PV₂S₁₀ was obtained by heating the elements in stoichiometric proportions at 490°C in evacuated Pyrex tubes. The crystal symmetry is monoclinic, space group $\text{P2}{}_1\text{c}$, with the unit cell parameters a = 12.734(8)Å, b = 7.349(7)Å, c = 23.662(4)Å, β = 95°22(1), V = 2205(4)ų, and Z = 8. The structure was solved from 2269 independant reflexions, and anisotropic least squares refinement gave R = 0.036 with 236 variables. The structure can be described as made of [V₂S₁₂] units forming endless chains themselves linked, two by two, by [PS₄] tetrahedra. In these units each vanadium is surrounded by eight sulfur atoms (mean d_VS = 2.459Å) arranged in a distorted bicapped triangular prism. Two of these prisms shared a rectangular face to form [V₂S₁₂] groups, in which intercationic distances implied vanadium-vanadium bonds (mean d_VV = 2.852(2)Å). Between the infinite double chains, only SS weak van der Waals' bonds exist. More than two thirds of the sulfur atoms are present as [SS]^?II pairs, (mean d_SS = 2.015Å); the rest are S^?II anions.     

Toward glasses with better indentation cracking resistance

The microcracking sequence (radial, median, lateral, and ring-like) arising at the glass surface under sharp contact loading and the extent to which these cracks develop is intimately related to the way the material attempts to relax the corresponding stress field. Two processes which are known to occur upon indentation are densification and isochoric shear flow. The contributions of both mechanisms were quantitatively assessed for glasses belonging to different chemical systems in previous papers ,  and . In the present study, indentation cracking maps are provided, which offer guidelines to the design of glasses with better surface damage resistance based on their elastic properties and hardness.     

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.     

From Graftable Biphotonic Chromophores to Water‐Soluble Organic Nanodots for Biophotonics: The Importance of Environmental Effects

The photophysical and two‐photon absorption (TPA) properties of biphotonic chromophores with one or two phenol pendant units were studied and compared with that of a model biphotonic quadrupolar chromophore. A water‐soluble dendritic structure was then synthesized by using the pendant moieties as starting points for the construction of dendritic branches. We show that the polarity of the environment significantly modulates both the fluorescence and the TPA responses of the different chromophoric derivatives. This extends to more subtle effects that involve phenol pendant moieties that were found to act as discrete solvating units and to modify both the photophysics and the TPA response of the chromophore. This demonstrates the high sensitivity of the TPA response of quadrupolar derivatives to minute alterations in the environment. Moreover, the dendritic branches were found to behave as a peculiar cybotactic environment that was able to tune the fluorescence and TPA response of the inner chromophore by creating a polar environment. This reveals a new direction for exploiting such effects by playing on the dendritic architecture (e.g., the nature and shape of the building blocks, the geometry and position of the chromophore) to modulate the TPA responses.     

Crystal and electronic band structure of IrTe2: Evidence of anionic bonds in a CdI2-like arrangement

The Rietveld structure determination of IrTe₂ showed that this phase differs from the CdI₂?like arrangement, with Te–Te multiple bonds (mean d_Te-Te = 3.528 Å) corresponding to Te^?1.5 anions, in agreement with the charge balance Ir³⁺(Te^?1.5)₂, the Iridium ion being d⁶ low spin. This new polymeric-CdI₂ structural type is shared by several other tellurides, namely: RhTe₂, CoTe_1.7, NiTe_1-x, PdTe₂, and PtTe₂, and its occurrence explains the abnormally low c/a ratio (1.38) of the hexagonal cell parameters. IrTe₂ band structure shows a strong degree of hybridization and mixing between the d cationic and p anionic levels. From the negative total overlap population between neighbour Ir³⁺ cations at the Fermi level, it can be inferred that the metallic conductivity of the phase involves the Tellurium anions through their 3D network. The crystal orbital overlap population curves for the Te–Te bonds indicate that electrons donated to the compound should fill anti-bonding levels, allowing for a breaking of these links, and possibly restoring a classical anionic stacking.     

Etude structurale des composés MxTiSe2 (M = Fe,Co, Ni)

New compounds M_xTiSe₂ have been prepared with M = Fe (x ? 0.66), M = Co or Ni (x ? 0.50). The metal M is located in vacant octahedral sites of the TiSe₂ host lattice (hexagonal unit cell a′, c′). An ordering of vacancies occurs if x ? 0.20. With M = Co or Ni (x = 0.50) and with M = Fe (0.25 ? x ? 0.66) isotypic compounds of Ti₃Se₄ can be obtained (M₃ □ X₄ type; monoclinic unit cell a ≈ a′ √3, b ≈ a′, c ≈ 2c′). The compounds Fe_0.38TiSe₂ and Co_0.38TiSe₂ (hexagonal unit cell a ≈ a′ √3, c ≈ 2c′) are of the M₂ □ X₃ type, variety 2c′. The Fe_0.25TiSe₂ and Co_0.25TiSe₂ monoclinic unit cells (a ≈ 2a′ √3, b ≈ 2a′, c ≈ 2c′) allow us to assume, for these two compounds, a structure of the M₅ □ ₃X₈ type, variety 2c′, identical to the Ti₅Se₈ one. The compound Ni_0.25TiSe₂ has an hexagonal unit cell (a ≈ 2a′, c ≈ 3c′); it belongs to a so-called 3c′ variety of the M₅ □ ₃X₈ type.     

Structural aspects and magnetic properties of the lamellar compound Cu0.50Cr0.50PS3

Cu_0.50Cr_0.50PS₃ is a new lamellar compound obtained from the elements at 700°C in evacuated silica tubes. The unit cell is monoclinic with a = 5.916 (1) Å; b = 10.246 (2) Å; c = 13.415 (5) Å; β = 107.09 (3)°. The structure is built up with S|Cu_0.33Cr_0.33(P₂)_0.33|S slabs in which copper, chromium, and (P₂) pairs share the octahedral voids between two sulfur layers. Copper is not located at the center of its octahedral sites but is distributed among a continuous series of positions within these sites. This complex distribution has been simulated, attributing to copper two crystallographic eightfold positions with important thermal factors, especially perpendicular to the a-b plane. EPR studies and optical and magnetic measurements show that chromium is present as Cr³⁺ ions. The magnetic study suggests that, below T_N ～ 30 K, this compound is a weakly anisotropic antiferromagnet consisting possibly of ferromagnetic layers which are antiferromagnetically coupled to adjacent layers. A good fit with the experimental results is obtained by means of calculations performed on the basis of a two-dimensional Heisenberg model.     

Sur un diagramme ionicité-structure pour les composes intercalaires alcalins des sulfures lamellaires

The structure of alkali-metal intercalation compounds in layer disulfide host lattices is discussed. The sulfur surrounding of the alkali-metal (octahedral or trigonal prismatic) is a function of the size of the A⁺ ion, the amount of intercalated atoms, and the nature of the TS bond. It is possible to study the relationship between the structural models and the ionicity of the bonds. Such a diagram could be used to predict the structures to be expected. A discussion of the second stage phases is given.