Investigating the Mechanism and Electrode Kinetics of the Oxygen vertical bar Superoxide (O-2 vertical bar O-2(center dot-)) Couple in Various Room-Temperature Ionic Liquids at Gold and Platinum Electrodes in the Temperature Range 298-318 K

The reduction of oxygen was studied over a range of temperatures (298-318 K) in n-hexyltriethylammonium bis(trifluoromethanesulfonyl)imide, [N-6,N-2,N-2,N-2][NTf2], and 1-butyl-2,3-methylimidazolium bis(trifluoromethanesulfonyl)imide, [C(4)dmim][NTf2] on both gold and platinum microdisk electrodes, and the mechanism and electrode kinetics of the reaction investigated. Three different models were used to simulate the CVs, based on a simple electron transfer ('E'), an electron transfer coupled with a reversible homogeneous chemical step ('ECrev') and an electron transfer followed by adsorption of the reduction product ('EC(ads)'), and where appropriate, best fit parameters deduced, including the heterogeneous rate constant, formal electrode potential, transfer coefficient, and homogeneous rate constants for the ECrev mechanism, and adsorption/desorption rate constants for the EC(ads) mechanism. It was concluded from the good simulation fits on gold that a simple E process operates for the reduction of oxygen in [N-6,N-2,N-2,N-2][NTf2], and an ECrev process for [C(4)dmim][NTf2], with the chemical step involving the reversible formation of the O-2(center dot-)center dot center dot center dot [C(4)dmim](+) ion-pair. The E mechanism was found to loosely describe the reduction of oxygen in [N-6,N-2,N-2,N-2][NTf2] on platinum as the simulation fits were reasonable although not perfect, especially for the reverse wave. The electrochemical kinetics are slower on Pt, and observed broadening of the oxidation peak is likely due to the adsorption of superoxide on the electrode surface in a process more complex than simple Langmuirian. In [C(4)dmim][NTf2] the O-2(center dot-) predominantly ion-pairs with the solvent rather than adsorbs on the surface, and an ECrev quantitatively describes the reduction of oxygen on Pt also.

Characterization of silica-supported dodecatungstic heteropolyacids as a function of their dehydroxylation temperature

Dodecatungsto-silicic H4SiW12O40 and -phosphoric acids H3PW12O40 were deposited on silica by a classical impregnation technique. The resulting materials were studied by in situ Raman and infrared spectroscopy, XPS and by solid-state H-1 MAS NMR as a function of their dehydroxylation temperature. The data show that in the case of H3PW12O40 three silanol groups are protonated while in the case of H4SiW12O40 at least one acidic proton remains. Upon heating this proton reacts leading to a disordered structure and a broadening of the W-O Raman bands.

The Effect of Antinotches on Domain Wall Mobility in Single Crystal Ferroelectric Nanowires

Changes in domain wall mobility, caused by the presence of antinotches in single crystal BaTiO3 nanowires, have been investigated. While antinotches appeared to cause a slight broadening in the distribution of switching events, observed as a function of applied electric field (inferred from capacitance-voltage measurements), the effect was often subtle. Greater clarity of information was obtained from Rayleigh analysis of the capacitance variation with ac field amplitude. Here the magnitude of the domain wall mobility parameter (R) associated with irreversible wall movements was found to be reduced by the presence of antinotches - an effect which became more noticeable on heating toward the Curie temperature. The reduction in this domain wall mobility was contrasted with the noticeable enhancement found previously in ferroelectric wires with notches. Finite element modeling of the electric field, developed in the nanowires during switching, revealed regions of increased and decreased local field at the center of the notch and antinotch structures, respectively; the absolute magnitude of field enhancement in the notch centers was considerably greater than the field reduction in the center of the antinotches and this was commensurate with the manner in, and degree to, which domain wall mobility appeared to be affected. We therefore conclude that the main mechanism by which morphology alters the irreversible component of the domain wall mobility in ferroelectric wire structures is via the manner in which morphological variations alter the spatial distribution of the electric field.

The spin-orbit alignment of the transiting exoplanet WASP-3b from Rossiter-McLaughlin observations

We present an observation of the Rossiter-McLaughlin effect for the planetary system WASP-3. Radial velocity measurements were made during transit using the SOPHIE spectrograph at the 1.93-m telescope at Haute-Provence Observatory. The shape of the effect shows that the sky-projected angle between the stellar rotation axis and planetary orbital axis (?) is small and consistent with zero within . WASP-3b joins the ~two-thirds of planets with measured spin-orbit angles that are well aligned and are thought to have undergone a dynamically gentle migration process such as planet-disc interactions. We find a systematic effect which leads to an anomalously high determination of the projected stellar rotational velocity (vsini = 19.6+2.2-2.1kms-1) compared to the value found from spectroscopic line broadening (vsini = 13.4 +/- 1.5kms-1). This is thought to be caused by a discrepancy in the assumptions made in the extraction and modelling of the data. Using a model developed by Hirano et al. designed to address this issue, we find vsini to be consistent with the value obtained from spectroscopic broadening measurements (vsini = 15.7+1.4-1.3kms-1).

Resonant positron annihilation in ammonia

Positron annihilation in ammonia is analyzed using the framework of resonant annihilation [G. F. Gribakin and C. M. R. Lee, Phys. Rev. Lett. 97, 193201 (2006)]. In particular, we show that molecular rotations can have a measurable e?ect on the annihilation rates at room temperatures. Rotation leads to broadening of vibrational Feshbach resonances. Rotations also allow a distinct contribution at low positron energies in the form of a rotational Feshbach resonance. This resonance can enhance the annihilation rate for thermalized room-temperature positrons. Comparison of theory and experiment shows that overtone and combination vibrations, including those due to inversion doubling, likely play an important role.

Positron-molecule interactions: Resonant attachment, annihilation, and bound states

This article presents an overview of current understanding of the interaction of low-energy positrons with molecules with emphasis on resonances, positron attachment, and annihilation. Measurements of annihilation rates resolved as a function of positron energy reveal the presence of vibrational Feshbach resonances (VFRs) for many polyatomic molecules. These resonances lead to strong enhancement of the annihilation rates. They also provide evidence that positrons bind to many molecular species. A quantitative theory of VFR-mediated attachment to small molecules is presented. It is tested successfully for selected molecule (e.g., methyl halides and methanol) where all modes couple to the positron continuum. Combination and overtone resonances are observed and their role is elucidated. Molecules that do not bind positrons and hence do not exhibit such resonances are discussed. In larger molecules, annihilation rates from VFR far exceed those explicable on the basis of single-mode resonances. These enhancements increase rapidly with the number of vibrational degrees of freedom, approximately as the fourth power of the number of atoms in the molecule. While the details are as yet unclear, intramolecular vibrational energy redistributio (IVR) to states that do not couple directly to the positron continuum appears to be responsible for these enhanced annihilation rates. In connection with IVR, experimental evidence indicates that inelastic positron escape channels are relatively rare. Downshifts of the VFR from the vibrational mode energies, obtained by measuring annihilate rates as a function of incident positron energy, have provided binding energies for 30 species. Their dependence upon molecular parameters and their relationship to positron-atom and positron-molecule binding-energy calculations are discussed. Feshbach resonances and positron binding to molecules are compared with the analogous electron-molecul (negative-ion) cases. The relationship of VFR-mediated annihilation to other phenomena such as Doppler broadening of the gamma-ray annihilation spectra, annihilation of thermalized positrons in gases, and annihilation-induced fragmentation of molecules is discussed. Possible areas for future theoretical and experimental investigation are also discussed.

Modulational instability and localized excitations involving two nonlinearly coupled upper-hybrid waves in plasmas

The nonlinear coupling between two perpendicularly propagating ( with respect to the external magnetic field direction) upper-hybrid ( UH) waves in a uniform magnetoplasma is considered, taking into account quasi-stationary density perturbations which are driven by the UH wave ponderomotive force. This interaction is governed by a pair of coupled nonlinear Schrodinger equations ( CNLSEs) for the UH wave envelopes. The CNLSEs are used to investigate the occurrence of modulational instability. Waves in the vicinity of the UH resonance are considered, so that the group dispersion terms for both waves are approximately equal, but the UH wave group velocities may be different. It is found that a pair of unstable UH waves ( obeying anomalous group dispersion) yields an increased instability growth rate, while a pair of stable UH waves ( individually obeying normal group dispersion) remains stable for equal group velocities, although it is destabilized by a finite group velocity mismatch. Stationary nonlinear solutions of the CNLSEs are presented.

Dynamics of nonlinearly coupled magnetic-field-aligned electromagnetic electron-cyclotron waves near the zero-group-dispersion point in magnetized plasmas

The nonlinear coupling between two magnetic-field-aligned electromagnetic electron-cyclotron (EMEC) waves in plasmas is considered. Evaluating the ponderomotive coupling between the EMEC waves and quasistationary plasma density perturbations, a pair of coupled nonlinear Schrodinger equations (CNLSEs) is obtained. The CNLSEs are then used to investigate the occurrence of modulational instability in magnetized plasmas. Waves in the vicinity of the zero-group-dispersion point are considered, so that the group dispersion terms may either bear the same or different signs. It is found that a stable EMEC wave can be destabilized due to its nonlinear interactions with an unstable one, while a pair of unstable EMEC waves yields an increased instability growth rate. Individually stable waves remain stable while interacting with one another. Stationary nonlinear solutions of the coupled equations are presented. The relevance of our investigation to nonlinear phenomena in space plasmas is discussed. (c) 2005 American Institute of Physics.

Nonlinearly coupled whistlers and dust-acoustic perturbations in dusty plasmas

The nonlinear interaction between magnetic-field-aligned coherent whistlers and dust-acoustic perturbations (DAPs) in a magnetized dusty plasma is considered. The interaction is governed by a pair of equations consisting of a nonlinear Schrodinger equation for the modulated whistler wave packet and an equation for the nonresonant DAPs in the presence of the ponderomotive force generated by the whistlers. The coupled equations are employed to investigate the occurrence of modulational instability, in addition to the formation of whistler envelope solitons. This investigation is relevant to amplitude modulated electron whistlers in magnetized space dusty plasmas. (c) 2005 American Institute of Physics.

Magnetization of left-handed metamaterials

We propose a possible mechanism for the generation of magnetic fields in negative refraction index composite metamaterials. Considering the propagation of a high-frequency modulated amplitude electric field in a left-handed material (LHM), we show that the ponderomotive interaction between the field and low-frequency potential distributions leads to spontaneous generation of magnetic fields, whose form and properties are discussed.

Evolution of linearly polarized electromagnetic pulses in laser plasmas

An analytical and numerical investigation is presented of the behavior of a linearly polarized electromagnetic pulse as it propagates through a plasma. Considering a weakly relativistic regime, the system of one-dimensional fluid-Maxwell equations is reduced to a generalized nonlinear Schrodinger type equation, which is solved numerically using a split step Fourier method. The spatio-temporal evolution of an electromagnetic pulse is investigated. The evolution of the envelope amplitude of density harmonics is also studied. An electromagnetic pulse propagating through the plasma tends to broaden due to dispersion, while the nonlinear frequency shift is observed to slow down the pulse at a speed lower than the group velocity. Such nonlinear effects are more important for higher density plasmas. The pulse broadening factor is calculated numerically, and is shown to be related to the background plasma density. In particular, the broadening effect appears to be stronger for dense plasmas. The relation to existing results on electromagnetic pulses in laser plasmas is discussed. (c) 2008 American Institute of Physics.

Behaviour of joints with bonded-in steel bars loaded parallel to the grain of timber elements

Within the sustainability context, this paper is extremely timely and relevant. The research focuses on broadening the use of timber structurally. The insight gained forms the basis for sustainable, fire resistant, economic and aesthetically pleasing moment resistant connections in timber.

The Oscillations of Tau Pegasi

We present extensive spectroscopic time series observations of the multiperiodic, rapidly rotating, delta Scuti star tau Pegasi. Information about the oscillations is contained within the patterns of line-profile variation of the star's blended absorption-line spectrum. We introduce the new technique of Doppler deconvolution with which to extract these patterns by modeling the intrinsic stellar spectrum and the broadening functions for each spectrum in the time series. Frequencies and modes of oscillation are identified from the variations using the technique of Fourier-Doppler imaging and a two-dimensional least-squares cleaning algorithm. We find a rich mode spectrum with degrees up to l = 20 and with frequencies below about 35 cycles day-1. Those modes with the largest amplitudes have frequencies that lie within a narrow band. We conclude that the observed spectrum can be explained if the modes of tau Peg propagate in the prograde direction with l ~= |m| and with frequencies that are about equal in the corotating frame of the star. We discuss the implications of these results for the prospect of delta Scuti seismology.

WASP-23b: a transiting hot Jupiter around a K dwarf and its Rossiter-McLaughlin effect

We report the discovery of a new transiting planet in the southern hemisphere. It was found by the WASP-south transit survey and confirmed photometrically and spectroscopically by the 1.2 m Swiss Euler telescope, LCOGT 2m Faulkes South Telescope, the 60 cm TRAPPIST telescope, and the ESO 3.6 m telescope. The orbital period of the planet is 2.94 days. We find that it is a gas giant with a mass of 0.88 ± 0.10 MJ and an estimated radius of 0.96 ± 0.05 RJ. We obtained spectra during transit with the HARPS spectrograph and detect the Rossiter-McLaughlin effect despite its small amplitude. Because of the low signal-to-noise ratio of the effect and a small impact parameter, we cannot place a strong constraint on the projected spin-orbit angle. We find two conflicting values for the stellar rotation. We find, via spectral line broadening, that v sin I = 2.2 ± 0.3 km s-1, while applying another method, based on the activity level using the index log R'_HK, gives an equatorial rotation velocity of only v = 1.35 ± 0.20 km s-1. Using these as priors in our analysis, the planet might be either misaligned or aligned. This result raises doubts about the use of such priors. There is evidence of neither eccentricity nor any radial velocity drift with time. Using WASP-South photometric observations confirmed with LCOGT Faulkes South Telescope, the 60 cm TRAPPIST telescope, the CORALIE spectrograph and the camera from the Swiss 1.2 m Euler Telescope placed at La Silla, Chile, as well as with the HARPS spectrograph, mounted on the ESO 3.6 m, also at La Silla, under proposal 084.C-0185. The data is publicly available at the CDS Strasbourg and on demand to the main author.RV data is only available at the CDS via anonymous ftp to cdsarc.u-strasbg.fr (130.79.128.5) or via http://cdsarc.u-strasbg.fr/viz-bin/qcat?J/A+A/531/A24Appendix is available in electronic form at http://www.aanda.org

Polar distribution of ablated atomic material during the pulsed laser deposition of Cu in vacuum: Dependence on focused laser spot size and power density

Experiments have been carried out to investigate the polar distribution of atomic material ablated during the pulsed laser deposition of Cu in vacuum. Data were obtained as functions of focused laser spot size and power density. Thin films were deposited onto flat glass substrates and thickness profiles were transformed into polar atomic flux distributions of the form f(theta)=cos(n) theta. At constant focused laser power density on target, I=4.7+/-0.3X10(8) W/cm(2), polar distributions were found to broaden with a reduction in the focused laser spot size. The polar distribution exponent n varied from 15+/-2 to 7+/-1 for focused laser spot diameter variation from 2.5 to 1.4 mm, respectively, with the laser beam exhibiting a circular aspect on target. With the focused laser spot size held constant at phi=1.8 mm, polar distributions were observed to broaden with a reduction in the focused laser power density on target, with the associated polar distribution exponent n varying from 13+/-1.5 to 8+/-1 for focused laser power density variation from 8.3+/-0.3X10(8) to 2.2+/-0.1X10(8) W/cm(2) respectively. Data were compared with an analytical model available within the literature, which correctly predicts broadening of the polar distribution with a reduction in focused laser spot size and with a reduction in focused laser power density, although the experimentally observed magnitude was greater than that predicted in both cases. (C) 1996 American Institute of Physics.