Strongly coupled chameleons and the neutronic quantum bouncer

We consider the potential detection of chameleons using bouncing ultracold neutrons. We show that the presence of a chameleon field over a planar plate would alter the energy levels of ultracold neutrons in the terrestrial gravitational field. When chameleons are strongly coupled to nuclear matter, β?10(8), we find that the shift in energy levels would be detectable with the forthcoming GRANIT experiment, where a sensitivity of the order of 1% of a peV is expected. We also find that an extremely large coupling β?10(11) would lead to new bound states at a distance of order 2 μm, which is already ruled out by previous Grenoble experiments. The resulting bound, β?10(11), is already 3 orders of magnitude better than the upper bound, β?10(14), from precision tests of atomic spectra.     

Layered hydroxide hybrid nanostructures: a route to multifunctionality

Today, seeking new materials for tailor-made applications and new devices leads to explore the potential offered by various kinds of functional building blocks. Hence, it concerns not only solid-state chemists, physicists or materials engineers, but also the area of (supra)molecular chemistry, and biochemistry as well. This is especially clear in the field of hybrid multifunctional materials. Indeed, their design requires investigating new concepts derived from principles developed in these different disciplines. The aim of this critical review is to present the last achievements concerning transition metal hydroxide hybrids, their synthesis, flexibility and functional properties. They often provide nice model systems for understanding the correlation between structure and physical properties brought by the molecular moieties grafted onto the metal hydroxide basis layers. The contribution of the atomic scale modelling to the electronic structure calculations and structural optimization is also reported (216 references).     

Ring-rearrangement metathesis of nitroso Diels-Alder cycloadducts

Strained nitroso Diels–Alder bicyclo[2.2.1] or [2.2.2] adducts functionalized with alkene side chains of diverse length undergo a ring‐rearrangement metathesis process with external alkenes and Grubbs II or Hoveyda–Grubbs II ruthenium catalysts, under microwave irradiation or classical heating, to deliver cis‐fused bicycles of various ring sizes, which contain a N? O bond. These scaffolds are of synthetic relevance for the generation of molecular diversity and to the total synthesis of alkaloids. The observation of unexpected reactions, such as epimerization or one‐carbon homologation of the alkene side chain, is also reported.     

Concise synthesis of pyrrolidine and indolizidine alkaloids by a highly convergent three-component reaction

The synthesis of pyrrolidine and indolizidine derivatives through radical carboazidation of alkenes with α-iodoketones, followed by reductive amination, is described. When properly substituted, further lactamization afforded pyrrolizidinones in good yield. This carboazidation/reductive amination sequence was efficiently applied to the total synthesis of three different simple alkaloids, including (±)-monomorine I.     

Probing the dynamics of CO2 and CH4 within the porous zirconium terephthalate UiO-66(Zr): a synergic combination of neutron scattering measurements and molecular simulations

Quasi-elastic neutron scattering (QENS) measurements combined with molecular dynamics (MD) simulations were conducted to deeply understand the concentration dependence of the self- and transport diffusivities of CH(4) and CO(2), respectively, in the humidity-resistant metal-organic framework UiO-66(Zr). The QENS measurements show that the self-diffusivity profile for CH(4) exhibits a maximum, while the transport diffusivity for CO(2) increases continuously at the loadings explored in this study. Our MD simulations can reproduce fairly well both the magnitude and the concentration dependence of each measured diffusivity. The flexibility of the framework implemented by deriving a new forcefield for UiO-66(Zr) has a significant impact on the diffusivity of the two species. Methane diffuses faster than CO(2) over a broad range of loading, and this is in contrast to zeolites with narrow windows, for which opposite trends were observed. Further analysis of the MD trajectories indicates that the global microscopic diffusion mechanism involves a combination of intracage motions and jump sequences between tetrahedral and octahedral cages.     

Free convolution operators and free Hall transform

We define an extension of the polynomial calculus on a W^?$W^{?}$-probability space by introducing an algebra C{_Xi:i∈I}$\mathbb{C}\{X_i:i\in I\}$ which contains polynomials. This extension allows us to define transition operators for additive and multiplicative free convolution. It also permits us to characterize the free Segal–Bargmann transform and the free Hall transform introduced by Biane, in a manner which is closer to classical definitions. Finally, we use this extension of polynomial calculus to prove two asymptotic results on random matrices: the convergence for each fixed time, as N   tends to ∞, of the ?-distribution of the Brownian motion on the linear group _GLN(C)${\mathit{GL}}_N(\mathbb{C})$ to the ?-distribution of a free multiplicative circular Brownian motion, and the convergence of the classical Hall transform on U(N)$U(N)$ to the free Hall transform.     

Macroscopic model of multicomponent fluids in porous media

This article is about a macroscopic model simulating the heat and mass transfer of a fluid containing numerous species in porous media. In order to use it in the modelling of petroleum fields, the physical phenomena studied are gravitational segregation, thermal diffusion, convection and diffusion. The originality of this approach is to simulate the movement of each component in order to deduce the species distribution and mixture flow. The mass flux calculated by an entropic balance is compared with the Darcy equation to evaluate the phenomenological coefficients. After presenting the possible origins of composition variations and the ways that they are usually studied, the article describes the developments that have led to the new model and finally reports the first results obtained.     

Hyper‐Raman and Raman scattering in paratellurite TeO2

Raman spectra of the tetragonal structure of paratellurite TeO₂ have been revisited avoiding anomalous polarization‐selection‐rules violations previously observed and due to optical activity. We present a complementary hyper‐Raman scattering study of paratellurite. Wavenumber and symmetry assignments are given for all expected 21 Raman active optical branches, except one LO component (out of the eight expected TO–LO pairs) of the polar doublet E modes. Also, the four expected hyper‐Raman active A₂ (TO) modes have been observed. Moreover, we have observed a strong Kleinman‐disallowed hyper‐Rayleigh signal, which is tentatively assigned as a first evidence of hyper‐Rayleigh optical activity. Copyright © 2013 John Wiley & Sons, Ltd.