Study by Optical Spectroscopy of Bismuth Emission in a Nanosecond-Pulsed Discharge Created in Liquid Nitrogen

Time-resolved optical emission spectroscopy of nanosecond-pulsed discharges ignited in liquid nitrogen between two bismuth electrodes is used to determine the main discharge parameters (electron temperature, electron density and optical thickness). Nineteen lines belonging to the Bi I system and seven to the Bi II system could be recorded by directly plunging the optical fibre into the liquid in close vicinity to the discharge. The lack of data for the Stark parameters to evaluate the broadening of the Bi I lines was solved by taking advantage of the time-resolved information supported by each line to determine them. The electron density was found to decrease exponentially from 6.5 ± 1.5 × 10¹⁶ cm⁻³ 200 ns after ignition to 1.0 ± 0.5 × 10¹⁶ cm⁻³ after 1050 ns. The electron temperature was found to be 0.35 eV, close to the value given by Saha’s equation.     

Design and evaluation of a crystalline hybrid of molecular conductors and molecular rotors

Combining recent concepts from the fields of molecular conductivity and molecular machinery we set out to design a crystalline molecular conductor that also possesses a molecular rotor. We report on the structures, electronic and physical properties, and dynamics of two solids with a common 1,4-bis(carboxyethynyl)bicyclo[2.2.2]octane (BABCO) functional rotor. One, [nBu(4)N(+)](2)[BABCO][BABCO(-)](2), is a colorless insulator where the dicarboxylic acid cocrystallizes with two of its monoanionic conjugated bases. The other is self-assembled by electrocrystallization in the form of black, shiny needles, with highly conducting molecular slabs of (EDT-TTF-CONH(2))(2)(+) (EDT-TTF = ethylenedithiotetrathiafulvalene) and anionic [BABCO(-)] rotors. Using variable-temperature (5-300 K) proton spin-lattice relaxation, (1)H T(1)(-1), we were able to assign two types of Brownian rotators in [nBu(4)N(+)](2)[BABCO][BABCO(-)](2). We showed that neutral BABCO groups have a rotational frequency of 120 GHz at 300 K with a rotational barrier of 2.03 kcal mol(-1). Rotors on the BABCO(-) sites experience stochastic 32 GHz jumps at the same temperature over a rotational barrier of 2.72 kcal mol(-1). In contrast, the BABCO(-) rotors within the highly conducting crystals of (EDT-TTF-CONH(2))(2)(+)[BABCO(-)] are essentially "braked" at room temperature. Notably, these crystals possess a conductivity of 5 S cm(-1) at 1 bar, which increases rapidly with pressure up to 50 S cm(-1) at 11.5 kbar. Two regimes with different activation energies E(a) for the resistivity (180 K above 50 and 400 K below) are observed at ambient pressure; a metallic state is stabilized at ca. 8 kbar, and an insulating ground state remains below 50 K at all pressures. We discuss two likely channels by which the motion of the rotors might become slowed down in the highly conducting solid. One is defined as a low-velocity viscous regime inherent to a noncovalent, physical coupling induced by the cooperativity between five C(sp3)-H···O hydrogen bonds engaging any rotor and five BABCO units in its environment. The rotational barrier calculated with the effect of this set of hydrogen bonds amounts to 7.3 kcal mol(-1). Another is quantum dissipation, a phenomenon addressing the difference of dynamics of the rotors in the two solids with different electrical properties, by which the large number of degrees of freedom of the low dimensional electron gas may serve as a bath for the dissipation of the energy of the rotor motion, the two systems being coupled by the Coulomb interaction between the charges of the rotors (local moments and induced dipoles) and the charges of the carriers.     

On the Dynamics of Bohmian Measures

The present work is devoted to the study of dynamical features of Bohmian measures, recently introduced by the authors. We rigorously prove that for sufficiently smooth wave functions the corresponding Bohmian measure furnishes a distributional solution of a nonlinear Vlasov-type equation. Moreover, we study the associated defect measures appearing in the classical limit. In one space dimension, this yields a new connection between mono-kinetic Wigner and Bohmian measures. In addition, we shall study the dynamics of Bohmian measures associated to so-called semi-classical wave packets. For these type of wave functions, we prove local in-measure convergence of a rescaled sequence of Bohmian trajectories towards the classical Hamiltonian flow on phase space. Finally, we construct an example of wave functions whose limiting Bohmian measure is not mono-kinetic but nevertheless equals the associated Wigner measure.     

From classical to semiclassical non-trapping behaviour

For the semiclassical Schrödinger operator with smooth long-range potential, we prove in a new way, making use of semiclassical measures, that the boundary values of its resolvent at non-trapping energies are bounded by O(1/h), h being the semiclassical parameter. To cite this article: T. Jecko, C. R. Acad. Sci. Paris, Ser. I 338 (2004).     

Ag2V4O11: from primary to secondary battery

Journal of Solid State Electrochemistry - Ag2V4O11 (silver vanadium oxide, SVO) is the positive electrode in primary lithium/SVO batteries that had known an extraordinary success as a power source...     

An explicit finite volume scheme on staggered grids for the Euler equations: Unstructured meshes,stability analysis,and energy conservation

We set up a numerical strategy for the simulation of the Euler equations, in the framework of finite volume staggered discretizations where numerical densities, energies, and velocities are stored on different locations. The main difficulty relies on the treatment of the total energy, which mixes quantities stored on different grids. The proposed method is strongly inspired, on the one hand, from the kinetic framework for the definition of the numerical fluxes, and, on the other hand, from the discrete duality finite volume (DDFV) framework, which has been designed for the simulation of elliptic equations on complex meshes. The time discretization is explicit and we exhibit stability conditions that guaranty the positivity of the discrete densities and internal energies. Moreover, while the scheme works on the internal energy equation, we can define a discrete total energy which satisfies a local conservation equation. We provide a set of numerical simulations to illustrate the behavior of the scheme.     

In situ characterization of undulator magnetic fields

A new in situ method is proposed to characterize the peak magnetic fields of undulator sources. The X‐ray beam emitted by the HU52 Apple‐2 undulator of the DEIMOS beamline of the SOLEIL synchrotron is analyzed using the Bragg diffraction of a Si(111) crystal. Measurements over the undulator gap range in linear horizontal polarization are compared with simulations in order to rebuild the Halbach function linking the undulator gaps to their peak magnetic fields. The method presented also allows information about the electron beam to be obtained.     

Biosensor employing screen‐printed PEDOT:PSS for sensitive detection of phenolic compounds in water

Poly(3,4‐ethylenedioxythiophene) (PEDOT) and its derivatives are relatively new, and unique members of conducting‐polymers family. In this article, we present an approach for simple, reliable and cost‐efficient electrochemical biosensor for real‐time detection and quantification of phenolic compounds (PhCs). The PEDOT:poly(styrene sulfonate) (PSS) polymer, directly screen‐printed on the surface of the working electrode, was shown to act as an effective electrical conductor but also as an efficient redox mediator. It has also been found suitable for the reduction of quinone ions at low reducing potentials, close to 0 V versus Ag/AgCl, thus minimizing interferences due to other electroactive species present in real samples. Based on these properties, a biosensor based on tyrosinase immobilized on PEDOT:PSS‐modified electrodes was developed allowing the detection of PhCs in surface waters. The biosensor displayed very good performance in terms of sensitivity, detection limit and linear range. Assays using surface water previously spiked with bisphenol A showed that the biosensor was able to detect PhCs in real conditions with no matrix effect. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Studies on the asymmetric Birch reductive alkylation to access spiroimines

The asymmetric Birch reductive alkylation has been investigated to synthesize spiroimine analogs of the neurophycotoxin (?)-gymnodimine A 1. Two types of chiral aromatic substrates, an acyclic benzamide 2 and a benzoxazepinone 3 were studied. We found that the chiral auxiliary of benzoxazepinone could be easily removed in a three step procedure to afford β-ketoester 14 that was converted into spiroimines 23–24 possessing antagonist effects on nicotinic acetylcholine receptors (nAChRs).