Symmetry-Breaking Charge-Transfer Chromophore Interactions Supported by Carbon Nanodots

Carbon dots (CDs) and their derivatives are useful platforms for studying electron-donor/acceptor interactions and dynamics therein. Herein, we couple amorphous CDs with phthalocyanines (Pcs) that act as electron donors with a large extended π-surface and intense absorption across the visible range of the solar spectrum. Investigations of the intercomponent interactions by means of steady-state and pump-probe transient absorption spectroscopy reveal symmetry-breaking charge transfer/separation and recombination dynamics within pairs of phthalocyanines. The CDs facilitate the electronic interactions between the phthalocyanines. Thus, our findings suggest that CDs could be used to support electronic couplings in multichromophoric systems and further increase their applicability in organic electronics, photonics, and artificial photosynthesis.     

O-Doped Nanographenes: A Pyrano/Pyrylium Route Towards Semiconducting Cationic Mixed-Valence Complexes

Herein we report an efficient synthesis to prepare O-doped nanographenes derived from the π-extension of pyrene. The derivatives are highly fluorescent and feature low oxidation potentials. Using electrooxidation, crystals of cationic mixed-valence (MV) complexes were grown in which the organic salts organize into face-to-face π-stacks, a favorable solid-state arrangement for organic electronics. Variable-temperature electron paramagnetic resonance (EPR) measurements and relaxation studies suggest a strong electron delocalization along the longitudinal axis of the columnar π-stacking architectures. Electric measurements of single crystals of the MV salts show a semiconducting behavior with a remarkably high conductivity at room temperature. These findings support the notion that π-extension of heteroatom-doped polycyclic aromatic hydrocarbons is an attractive approach to fabricate nanographenes with a broad spectrum of semiconducting properties and high charge mobilities.     

Multiscale clustering in granular surface flows

We investigate steady granular surface flows in a rotating drum and demonstrate the existence of rigid clusters of grains embedded in the flowing layer. These clusters appear to be fractal and their size is power law distributed from the grain size scale up to the thickness of the flowing layer. The implications of the absence of a characteristic length scale on available theoretical models of dense granular flows are discussed. Finally, we suggest a possible explanation of the difference between velocity profiles observed in surface flows and in flows down a rough inclined plane.     

Collisions and Fracture: a 1-D Theory. How to Tear off a Chandelier from the Ceiling

When a plate falls on the ground, it breaks. We study this phenomenon at the macroscopic level. We restrict ourselves to 1-D problems and illustrate the theory with a chandelier to which a falling stone is tied. The collisions are assumed instantaneous. Percussions are introduced at the unknown fracture points. Equations of motion and constitutive laws give a set of differential equations, whose corresponding variational problem may be solved in SBV (special functions of bounded variation). The example shows how the theory applies and gives realistic results.     

Spectroscopic study of the ν1 band of SO2 using a continuous-wave DFB QCL at 9.1 μm

We report results of spectroscopic measurements with a continuous-wave distributed-feedback quantum-cascade laser (DFB QCL). Line intensities and self-broadening coefficients were measured in the ₁ band of SO₂ between 1088 and 1090 cm^-1. The self-broadening coefficients in this paper confirm the typical decrease of _self with increasing rotational quantum number K_a . The line intensities determined here are smaller than those in the HITRAN 2000 database. Several lines found in this study were not present in the database. PACS 07.57.Ty; 33.20.Ea     

Well-posedness results for a model of damage in thermoviscoelastic materials

This paper deals with a phase transitions model describing the evolution of damage in thermoviscoelastic materials. The resulting system is highly non-linear, mainly due to the presence of quadratic dissipative terms and non-smooth constraints on the variables. Existence and uniqueness of a solution are proved, as well as regularity results, on a suitable finite time interval.     

Magnesium nanoparticles with transition metal decoration for hydrogen storage

We report on the hydrogen storage behaviour of Mg nanoparticles (NPs) (size range 100 nm–1 μm) with metal-oxide core–shell morphology synthesized by inert gas condensation and decorated by transition metal (TM) (Pd or Ti) clusters via in situ vacuum deposition. The structure and morphology of the as-prepared and hydrogenated NPs is studied by electron microscopy, X-ray diffraction including in situ experiments and X-ray absorption spectroscopy, in order to investigate the relationships with the hydrogen storage kinetics measured by the volumetric Sieverts method. With both Pd and Ti, the decoration deeply improves the hydrogen sorption properties: previously inert NPs exhibit complete hydrogenation with fast transformation kinetics, good stability and reversible gravimetric capacity that can attain 6 wt%. In the case of Pd-decoration, the occurrence of Mg–Pd alloying is observed at high temperatures and in dependence of the hydrogen pressure conditions. These structural transformations modify both the kinetics and thermodynamics of hydride formation, while Ti-decoration has an effect only on the kinetics. The experimental results are discussed in relation with key issues such as the amount of decoration, the heat of mixing between TM and Mg and the binding energy between TM and hydrogen.     

Huge Seebeck coefficients in nonaqueous electrolytes

The Seebeck coefficients of the nonaqueous electrolytes tetrabutylammonium nitrate, tetraoctylphosphonium bromide, and tetradodecylammonium nitrate in 1-octanol, 1-dodecanol, and ethylene-glycol are measured in a temperature range from T = 30?°C to T = 45?°C. The Seebeck coefficient is generally of the order of a few hundreds of microvolts per Kelvin for aqueous solution of inorganic ions. Here we report huge values of 7 mV/K at 0.1 M concentration for tetrabutylammonium nitrate in 1-dodecanol. These striking results open the question of unexpectedly large kosmotrope or "structure making" effects of tetraalkylammonium ions on the structure of alcohols.