Electron entanglement near a superconductor and bell inequalities

Near the interface between a normal metal and a superconductor, Cooper pairs penetrate into the normal side, giving rise to the proximity effect. The two electrons of these pairs have entangled spin and orbital degrees of freedom. Nonlocal features of quantum mechanics can be probed by separating these two electrons. This is achieved with a fork geometry with two normal leads containing either spin- or energy-selective filters. A signature of entanglement can be detected by measuring the positive noise cross-correlations in this fork. In the case of energy filters, Bell-inequality checks constitute a definite probe of entanglement. We formulate Bell-type inequalities in terms of current-current cross-correlations associated with contacts with varying magnetization orientations. We find maximal violation (as in photons) when a superconductor is the particle source.     

Polyphosphate ions encapsulated in oxothiomolybdate rings: synthesis, structure, and behavior in solution

Cyclic oxothiomolybdates containing polyphosphate ions were prepared by simple reactions in aqueous medium of the corresponding polyphosphate ions and the cyclic precursor K(2)I(2)Mo(10)S(10)O(10)(OH)(10)(OH(2))(5).15H(2)O. K(5)[Cl(P(2)O(7)]Mo(12)S(12)O(12)(OH)(12)(H(2)O)(4)].22H(2)O (1) was isolated from concentrated chloride solution (2.5 mol.L(-1)). 1 reveals a remarkable complex containing two different substrates encapsulated in a dodecanuclear ring, a H-bonded Cl(-) ion, and a covalently bonded [P(2)O(7)] group. The chloride ion in 1 can be selectively removed for a monohydrogenophosphate group yielding K(6)[(HPO(4))(P(2)O(7))Mo(12)S(12)O(12)(OH)(12)(H(2)O)(2)].19H(2)O (2), a mixed species containing a [P(2)O(7)] and a [HPO(4)] group. The substitution is accompanied by a significant change of the ring, which adopts a "pear-shape" conformation. In the presence of triphosphate ion, the "heart-shaped" decanuclear ring Rb(3)[(H(2)P(3)O(10))Mo(10)S(10)O(10)(OH)(10)].17.5H(2)O (3) is formed containing a linear [P(3)O(10)] group intimately embedded in the inorganic cyclic host. The three compounds were structurally characterized by single-crystal X-ray diffraction. The behaviors of 1, 2, and 3 in solution were studied by (31)P NMR. Variable temperature experiments, supported by a two-dimensional COSY (31)P experiment, revealed that the supramolecular interaction existing between the chloride ion and the ring in solid 1 is maintained in solution. Nevertheless, 1 remains labile, and successive equilibria were evidenced and interpreted as an ion-pair association involving a halide ion (Cl, Br, or I), responsible for the conformational change of the [P(2)O(7)] group within the cavity. The influence of the nature of the halide guest (Cl(-), Br(-), and I(-)) on the successive equilibria was studied, and the thermodynamic constant related to the postulated equilibrium was determined. The stability of the supramolecular association decreases in the order Cl > Br > I. In solution, a phosphate exchange is observed for 2 while for 3 the absence of temperature dependence of the (31)P NMR spectrum confirms the conformation of the host-guest system is blocked. Elemental analysis and infrared characterizations are also supplied.     

Size-selected synthesis of PtRu nano-catalysts: reaction and size control mechanism

A rapid synthesis method for the preparation of PtRu colloids and their subsequent deposition on high surface area carbons is presented. The reaction mechanism is shown to involve the oxidation of the solvent, ethylene glycol, to mainly glycolic acid or, depending on the pH, its anion, glycolate, while the Pt(+IV) and Ru(+III) precursor salts are reduced. Glycolate acts as a stabilizer for the PtRu colloids and the glycolate concentration, and hence the size of the resulting noble metal colloids is controlled via the pH of the synthesis solution. Carbon-supported PtRu catalysts of controlled size can be prepared within the range of 0.7-4 nm. Slow scan X-ray diffraction and high-resolution transmission electron microscopy show the PtRu catalysts to be crystalline. The Ru is partly dissolved in the face-centered cubic Pt lattice, but the catalysts also consist of a separate, hexagonal Ru phase. The PtRu catalysts appear to be of the same composition independent of the catalyst size in the range of 1.2-4 nm. Particular PtRu catalysts prepared in this work display enhanced activities for the CH(3)OH electro-oxidation reaction when compared to two commercial catalysts.     

Polyferrocenes: metallopolymers with tunable and high refractive indices

The refractive index, molar refraction and Abbe number of polyferrocene derivatives are reported and the values indicate that these materials are very promising for a range of photonics applications.     

Dynamic optimization and event location in atmospheric chemistry

A model coupling differential equations and an optimization problem with equality and inequality constraints is described. The first order optimality conditions are coupled with the differential equations to form a differential-algebraic system. Inequality constraints for the optimization variables induce discontinuities in the first derivatives of the solution in time. Tracking techniques based on sensitivity analysis and second order multistep methods are proposed to locate the discontinuities. Application to the dynamics of organic atmospheric aerosol particles is given to illustrate the detection of the activation of constraints. (© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Femtosecond Spectroscopy and Nonlinear Optical Properties of aza-BODIPY Derivatives in Solution

The fast relaxation processes in the excited electronic states of functionalized aza-boron-dipyrromethene (aza-BODIPY) derivatives ( 1 – 4 ) were investigated in liquid media at room temperature, including the linear photophysical, photochemical, and nonlinear optical (NLO) properties. Optical gain was revealed for nonfluorescent derivatives 3 and 4 in the near infrared (NIR) spectral range under femtosecond excitation. The values of two-photon absorption (2PA) and excited-state absorption (ESA) cross-sections were obtained for 1–4 in dichloromethane using femtosecond Z-scans, and the role of bromine substituents in the molecular structures of 2 and 4 is discussed. The nature of the excited states involved in electronic transitions of these dyes was investigated using quantum-chemical TD-DFT calculations, and the obtained spectral parameters are in reasonable agreement with the experimental data. Significant 2PA (maxima cross-sections ∼2000 GM), and large ESA cross-sections ∼10⁻²⁰ m² of these new aza-BODIPY derivatives 1–4 along with their measured high photostability reveal their potential for photonic applications in general and optical limiting in particular.     

A numerical study of vorticity layers in a two-dimensional stratified shear flow

A numerical study is conducted to find out the conditions of occurrence of a secondary Kelvin-Helmholtz instability in the thin layers (referred to as baroclinic layers) that form in a stably-stratified shear layer. For this purpose, three high resolution calculations of a moderately stratified shear layer have been carried out, at a fixed Reynolds number. The wavelength of the initial perturbation is progressively increased, starting from the fundamental wavelength predicted by linear stability theory up to twice this fundamental wavelength. The baroclinic layer of the flow is shown to lengthen and destabilize progressively from one calculation to the other, eventually bearing a secondary Kelvin-Helmholtz instability. The structure and dynamics of the baroclinic layers of the three calculations are examined in the frame of a theoretical model proposed by Corcos and Sherman ([1]). An excellent agreement with the predictions of this model have been found. We next show that the stability of the layer is controlled by the large-scale Kelvin-Helmholtz vortex, via the strain field that it induces in the stagnation point region of the layer. A consequence of this study is that secondary Kelvin-Helmholtz instabilities are fostered by the pairing of primary Kelvin-Helmholtz vortices in a strongly-stratified shear layer.

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Sommario E stato condotto uno studio numerico per trovare le condizioni in cui insorge una instabilità secondaria di Kelvin-Helmholtz negli strati sottili che si formano in uno strato di scorrimento stabilmente stratificato. A questo scopo sono state effettuate tre simulazioni ad alta risoluzione a fissato numero di Reynolds e stratificazione bassa. La lunghezza d'onda della perturbazione iniziale è stata progressivamente aumentata dalla lunghezza fondamentale predetta dalla teoria lineare della stabilità fino a due volte questa stessa lunghezza. È stato osservato che da una simulazione all'altra lo strato baroclino del flusso si allunga e si destabilizza progressivamente, generando eventualmente un'instabilità di Kelvin-Helmholtz secondaria. Utilizzando il modello teorico proposto da Corcos e Sherman (1976), per le tre simulazioni sono state analizzate la struttura e la dinamica dello strato baroclino. È stato trovato un accordo eccellente con le predizioni di questo modello. È stato in seguito mostrato che la stabilità dello strato è controllato dai vortici di Kelvin-Helmholtz di larga scala attraverso il campo di deformazione che inducono nella regione del punto di ristagno dello strato. Una conseguenza di questo studio è che le instabilità secondarie di Kelvin-Helmholtz sono forzate dall'accoppiamento dei vortici primari in uno strato di scorrimento fortemente stratificato.