Photomagnetic effect in a cyanide-bridged mixed-valence {Fe(II)2Fe(III)2} molecular square

The self-assembly of [Fe(III)(Tp)(CN)(3)](-) and [Fe(II)(bik)(2)(S)(2)](2+) affords the cyanide-bridged mixed valence {Fe(III)(2)Fe(II)(2)}(2+) molecular square, which exhibits a photomagnetic effect under laser light irradiation at low temperature and also shows thermal spin-state conversion near ambient temperature.     

Soft hollow particle damping identification in honeycomb structures

The aim of this study is to provide a structural damping solution for space applications to enhance mission performance of honeycomb structures. Classical particle dampers are enclosures partially filled with small metallic or glass spheres, attached to a vibrating structure. The induced damping mechanism is mainly due to frictional losses and collision effects. This paper deals with replacing classical hard particles with soft hollow ones. This study is oriented toward experimental investigations and theoretical validation in order to distinguish dissipation phenomena. The experimental approach first relies on identifying the damping in small honeycomb samples filled with particles. Instead of dissipation by friction and impact, the elliptical shape of the measured hysteresis loops highlights that visco-elastic behavior is dominant with these specific soft particle dampers. Then, experimental and numerical validations are performed on aluminum honeycomb cantilever beams filled with particles. To take into account the effect of the particles, equivalent oscillators, based on the previous experimental damping identification, are added to a finite element model. These kinds of particle dampers are highly nonlinear as a function of excitation frequency and amplitude. It is shown that good damping efficiency is achieved across a large frequency range with low impact on structure stiffness. This paper suggests a convenient method to model the structural damping induced by soft hollow particles.     

Templating of arrays of Ru nanoclusters by monolayer graphene/Ru Moirés with different periodicities

We have studied the formation of Ru nanocluster arrays on several monolayer graphene/Ru Moiré structures with different relative orientations of the graphene and Ru lattices. Experiments and ab initio calculations clearly show that the presence of a graphene/Ru Moiré does not guarantee the ordered adsorption of Ru nanoclusters. The simultaneous deposition of Ru onto coexisting Moirés demonstrates that a structure with aligned graphene and Ru lattices templates the formation of arrays of small Ru clusters with narrow size spread and adsorption exclusively in a single site (the 'low fcc' site). The other Moirés considered here gave rise to substantially larger clusters with broader size distribution and without detectable site selectivity. Calculations explain these findings via the density of states (DOS) at different sites of the graphene/Ru Moiré. The ordered nucleation of many small clusters instead of incorporation of metal atoms into larger ones requires one Moiré site with a large DOS at the Fermi level, so that the binding of metal adatoms to this site is stronger than to competing sites in the Moiré and to existing metal clusters.     

On the multifractal analysis of measures

The multifractal formalism is shown to hold for a large class of measures.     

Iota-carrageenan/casein micelles interactions: evidence at different scales

The effect of temperature on the behaviour of iota-carrageenan (CI) 0.1 wt.%/casein micelles (CM) 0–5 wt.% mixtures has been studied using three techniques: confocal laser scanning microscopy (CLSM), differential scanning calorimetry (DSC) and spectrophotometry. The microscopy clearly shows that those mixed systems separate in two phases, one being enriched in CM. It has been shown that the CM concentration seems to have an effect on the extent of the phase separation phenomenon. The DSC experiments show that addition of CM modifies the helix to coil transition temperature of carrageenan. The enthalpy of melting of helices decreases as the CM concentration increases, and the peak is shifted towards higher temperature. Local electrostatic interactions between carrageenan chains and CM have been studied by a spectrophotometric method using methylene blue (MB) properties of absorption. The absorption spectra of MB in presence of CI and CM were compared with the one of MB in presence of carrageenan alone at temperatures above and below the carrageenan coil to helix transition. The modifications of the spectrum by addition of CM are discussed in terms of interactions and rigidification of the carrageenan chains.     

Ab initio static and molecular dynamics study of 4-styrylpyridine.

We report an in‐depth theoretical study of 4‐styrylpyridine in its singlet S₀ ground state. The geometries and the relative stabilities of the trans and cis isomers were investigated within density functional theory (DFT) as well as within Hartree–Fock (HF), second‐order Møller–Plesset (MP2), and coupled cluster (CC) theories. The DFT calculations were performed using the B3LYP and PBE functionals, with basis sets of different qualities, and gave results that are very consistent with each other. The molecular structure is thus predicted to be planar at the energy minimum, which is associated with the trans conformation, and to become markedly twisted at the minimum of higher energy, which is associated with the cis conformation. The results of the calculations performed with the post‐HF methods approach those obtained with the DFT methods, provided that the level of treatment of the electronic correlation is high enough and that sufficiently flexible basis sets are used. Calculations carried out within DFT also allowed the determination of the geometry and the energy of the molecule at the biradicaloid transition state associated with the thermal cis?trans isomerization and at the transition states associated with the enantiomerization of the cis isomer and with the rotations of the pyridinyl and phenyl groups in the trans and cis isomers. Car–Parrinello molecular dynamics simulations were also performed at 50, 150, and 300 K using the PBE functional. The studies allowed us to evidence the highly flexible nature of the molecule in both conformations. In particular, the trans isomer was found to exist mainly in a nonplanar form at finite temperatures, while the rotation of the pyridinyl ring in the cis isomer was incidentally observed to take place within ≈1 ps during the simulation carried out at 150 K on this isomer.     

Ethene epoxidation selectivity inhibited by twisted oxametallacycle: a DFT study on Ag surface-oxide

Competitive ethene oxidation pathways are presented for a p(4 x 4) surface-oxide phase on Ag(111) obtained from density functional theory (DFT) calculations. Both parallel routes are found to proceed from a common oxametallacycle intermediate (OMME) in agreement with previous mechanistic studies on low coverage O adatom phase, although acetaldehyde (AcH) is favored by almost 2 kcal/mol. An even more striking difference with pure metal surface appears with the oxide regeneration pathways, which are found non-rate controlling. Furthermore, a kinetic model is developed on the basis of these DFT calculations and yields 96% selectivity in favor of AcH for a simulation in realistic catalytic conditions (600 K and respective partial pressures of 1 atm for ethene and oxygen reactants). As a key finding, this low ethene epoxide selectivity is proposed to be directly linked to the conformational barrier of the pivotal intermediate. In fact, the elasticity of the ultrathin oxide adlayer enables a twisted OMME structure as a true minimum, which agrees well with orbital prerequisite of the concerted H migration toward AcH. On the contrary, the desired selective ring closure forming ethene epoxide (EO) requires conformational inversion although the eclipsed form lies 2 kcal/mol above.     

Optically pumped14NH3 laser and its stark tuning at 10.78 μm

Infrared (ir) emissions from a TEA-CO₂-laser-pumped NH₃ laser are reported. Superfluorescent emissions and selective single-line oscillations have been obtained in the range from 11 to 13 m. The results make possible the design of a NH₃ Stark cell allowing a 1 GHz shift of the 10.78 m NH₃ emission line.     

Ligand-Driven Light-Induced Spin Change in Transition-Metal Complexes: Selection of an Appropriate System and First Evidence of the Effect, in Fe(II)(4-styrylpyridine)(4)(NCBPh(3))(2)

The first observation of a ligand-driven light-induced spin-state change (LD-LISC effect) in a transition-metal complex is reported. The compounds under investigation are of the type Fe(II)L(4)X(2), where L is a cis/trans photoisomerizable ligand. For an iron(II) spin-state change to result from ligand cis <--> trans conversion, the Fe(II)(trans-L)(4)X(2) species had to exhibit a thermally-induced high-spin state <--> low-spin state crossover. This property was checked by variable-temperature magnetic susceptibility measurements, for compounds with X(-) = NCBPh(3)(-) or NCBH(3)(-) and L = 1-phenyl-2-(4-pyridyl)ethene (or 4-styrylpyridine, abbreviated as Stpy), 1-(4-R-phenyl)-2-(4-pyridyl)ethene (R = CH(3), COOCH(3)), or 1-(1-naphthyl)-2-(4-pyridyl)ethene. The results are comparatively discussed. The best candidate for the LD-LISC effect to be observed is found to be Fe(Stpy)(4)(NCBPh(3))(2): the complex (C(t)) formed with trans-Stpy undergoes a thermally-induced spin crossover centered around 190 K; the one (C(c)) formed with cis-Stpy retains the high-spin state at any temperature. Photoisomerization of the Stpy ligand, at 140 K, in the complex embedded within a cellulose acetate matrix, is effectively shown, on the basis of UV-vis absorption measurements, to trigger the spin-state change of the iron(II) ions.     

Selective 1H-13C correlation by low power single frequency off-resonance decoupling assisted by exhaustive simulation techniques

Selectivity in the ¹H-¹³C correlation for assignments of ¹³C spectra is enhanced by recording single frequency off-resonance ¹³C NMR spectra with low decoupling field strength (? 2J_o), distortion of signal patterns is avoided by submitting the spin system to a previous noise broad band decoupling. Correlation is obtained by comparison of observed and simulated 2-D spectra (π ¹³C vs decoupler frequency) joined to fitting of the curve J_R = f (decoupler frequency) with the equation of Freeman and Anderson.₁