Determining concentration depth profiles in fluorinated networks by means of electric force microscopy

By means of electric force microscopy, composition depth profiles were measured with nanometric resolution for a series of fluorinated networks. By mapping the dielectric permittivity along a line going from the surface to the bulk, we were able to experimentally access to the fluorine concentration profile. Obtained data show composition gradient lengths ranging from 30 nm to 80 nm in the near surface area for samples containing from 0.5 to 5 wt. % F, respectively. In contrast, no gradients of concentration were detected in bulk. This method has several advantages over other techniques because it allows profiling directly on a sectional cut of the sample. By combining the obtained results with x-ray photoelectron spectroscopy measurements, we were also able to quantify F/C ratio as a function of depth with nanoscale resolution.     

Long-range-corrected hybrids using a range-separated Perdew-Burke-Ernzerhof functional and random phase approximation correlation

We build on methods combining a short-range density functional approximation with a long-range random phase approximation [B. G. Janesko, T. M. Henderson, and G. E. Scuseria, J. Chem. Phys. 130, 081105 (2009)] or second-order screened exchange [J. Paier et al., J. Chem. Phys. 132, 094103 (2010)] by replacing the range-separated local density approximation functional with a range-separated generalized gradient approximation functional in the short range. We present benchmark results that show a marked improvement in the thermodynamic tests over the previous local density approximation-based methods while retaining those methods' excellent performance in van der Waals interactions.     

Liquid-crystalline hybrid materials based on [60]fullerene and bent-core structures

What a core-ker! By the appropriate combination of promesogenic bent-core structures and the C(60) unit, lamellar polar liquid-crystal phases were induced. The supramolecular organization of the functional fullerene-based assemblies, the temperature range of the soft phase, the stabilization of the mesophase-like order at room temperature, and the molecular switching under an electric field can be tuned, depending on the molecular structure.     

Leading-Order Dynamics of Gravity-Driven Flows in?Free-Standing Soap Films

We derive the leading-order equations that govern the dynamics of the flow in a falling, free-standing soap film. Starting with the incompressible Navier?CStokes equations, we carry out an asymptotic analysis using parameters that correspond to a common experimental setup. We account for the effects of inertia, surface elasticity, pressure, viscous stresses, gravity, and air drag. We find that the dynamics of the flow is dominated by the effects of inertia, surface elasticity, gravity, and air drag. We solve the leading-order equations to compute the steady-state profiles of velocity, thickness, and pressure in an experiment in which the film is in the Marangoni elasticity regime. The computational results, which include a Marangoni shock, are in good accord with the experimental measurements.     

Spectral Shorted Operators

If $$\mathcal{H}$$ is a Hilbert space, $$\mathcal{S}$$ is a closed subspace of $$\mathcal{H},$$ and A is a positive bounded linear operator on $$\mathcal{H},$$ the spectral shorted operator $$\rho \left( {\mathcal{S},\mathcal{A}} \right)$$ is defined as the infimum of the sequence $$\sum (\mathcal{S},A^n )^{1/n} ,$$ where denotes $$\sum \left( {\mathcal{S},B} \right)$$ the shorted operator of B to $$\mathcal{S}.$$ We characterize the left spectral resolution of $$\rho \left( {\mathcal{S},\mathcal{A}} \right)$$ and show several properties of this operator, particularly in the case that dim $${\mathcal{S} = 1.}$$ We use these results to generalize the concept of Kolmogorov complexity for the infinite dimensional case and for non invertible operators.     

Microwave-promoted synthesis of chiral pyridinium salts

The synthesis of several chiral pyridinium salts via Zincke’s reaction can be easily accomplished by domestic microwave oven irradiation. Yield enhancements, reduction of reaction time, and less racemization were observed under microwave heating when compared to conventional heating in similar conditions.     

Theoretical predictions of the electronic and optical properties of single and coupled (In,Ga)As/GaAs quantum dots

We show how an atomistic pseudopotential plus many-body configuration interaction theory can address the main spectroscopic features of self-assembled dots including, excitons, trions, biexcitons, fine-structure, charging spectra as well as electric-field dependence of entanglement in dot molecules.     

Statistical Properties of Unimodal Maps

We consider typical analytic unimodal maps which possess a chaotic attractor. Our main result is an explicit combinatorial formula for the exponents of periodic orbits. Since the exponents of periodic orbits form a complete set of smooth invariants, the smooth structure is completely determined by purely topological data (“typical rigidity”), which is quite unexpected in this setting. It implies in particular that the lamination structure of spaces of analytic unimodal maps (obtained by the partition into topological conjugacy classes, see [ALM]) is not transversely absolutely continuous. As an intermediate step in the proof of the formula, we show that the distribution of the critical orbit is described by the physical measure supported in the chaotic attractor.     

Strategies for the synthesis of bi- and triarylic materials starting from commercially available phenols

A series of arylstannanes have been synthesized, through an S_RN1 mechanism, in good to excellent yields (74%-99%) by the photostimulated reaction of trimethyl stannyl ion with substrates supporting different nucleofugal groups. The arylstannanes thus obtained were suitable intermediates for Stille cross-coupling reactions leading to asymmetric bi- and triaryl compounds in acceptable global yields. An attractive feature of this route is that simple commercially available benzenediols, chloro- and methoxy phenols might be useful starting substrates, leading the latter to higher global yields of products in fewer steps. The strategies proposed open a broad synthetic tool.