Electrochemical ammonia gas sensing in nonaqueous systems: A comparison of propylene carbonate with room temperature ffonc liquids

First, the direct and indirect electrochemical oxidation of ammonia has been studied by cyclic voltammetry at glassy carbon electrodes in propylene carbonate. In the case of the indirect oxidation of ammonia, its analytical utility of indirect for ammonia sensing was examined in the range from 10 and 100 ppm by measuring the peak current of new wave resulting from reaction between ammonia and hydroquinone, as function of ammonia concentration, giving a sensitivity 1.29 x 10(-7) A ppm(-1) (r(2)=0.999) and limit-of-detection 5 ppm ammonia. Further, the direct oxidation of ammonia has been investigated in several room temperature ionic liquids (RTILs), namely 1-butyl-3-methylimidazolium tetrafluoroborate ([C(4)mim] [BF4]), 1-butyl-3-methylimiclazolium trifluoromethylsulfonate ([C4mim] [OTf]), 1-Ethyl -3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([C(2)mim] [NTf2]), 1-butyl-3-methylimidazolium bis(tritluoromethylsulfonyl)imide ([C4mim] [NTf2]) and 1-butyl-3-methylimidazolium hexafluorophosphate ([C4mim] [PF6]) on a 10 put diameter Pt microdisk electrode. In four of the RTILs studied, the cyclic voltammetric analysis suggests that ammonia is initially oxidized to nitrogen, N-2, and protons, which are transferred to an ammonia molecule, forming NH4+ via the protonation of the anion(s) (A(-)). However, in [C4mim] [PF6], the protonated anion was formed first, followed by NH4+. In all five RTILs, both HA and NH4+ are reduced at the electrode surface, forming hydrogen gas, which is then oxidized. The analytical ability of this work has also been explored further, giving a limit-of-detection close to 50 ppm in [C(2)mim] [NTf2], [C(4)mim] [OTf], [C(4)mim] [BF4], with a sensitivity of ca. 6 x 10(-7) A ppm(-1) (r(2) = 0.999) for all three ionic liquids, showing that the limit of detection was ca. ten times larger than that in propylene carbonate since ammonia in propylene carbonate might be more soluble in comparison with RTILs when considering the higher viscosity of RTILs.

Improved fault diagnosis in multivariate systems using regression-based reconstruction

Subspace monitoring has recently been proposed as a condition monitoring tool that requires considerably fewer variables to be analysed compared to dynamic principal component analysis (PCA). This paper analyses subspace monitoring in identifying and isolating fault conditions, which reveals that the existing work suffers from inherent limitations if complex fault senarios arise. Based on the assumption that the fault signature is deterministic while the monitored variables are stochastic, the paper introduces a regression-based reconstruction technique to overcome these limitations. The utility of the proposed fault identification and isolation method is shown using a simulation example and the analysis of experimental data from an industrial reactive distillation unit.

Quantum chessboards in the deuterium molecular ion

We present a new algorithm for vibrational control in deuterium molecules that is feasible with current experimental technology. A pump mechanism is used for creating a coherent superposition of the D-2(+) vibrations. A short, intense infrared control pulse is applied after a chosen delay time to create selective interferences. A 'chessboard' pattern of states can be realized in which a set of even- or odd-numbered vibrational states can be selectively annihilated or enhanced. A technique is proposed for experimental realization and observation of this effect using 5 fs pulses of lambda = 790 nm radiation, with intermediate intensity (5 x 10(13) W cm(-2)).

Inelastic quantum transport in nanostructures: The self-consistent Born approximation and correlated electron-ion dynamics

A dynamical method for inelastic transport simulations in nanostructures is compared to a steady-state method based on nonequilibrium Green's functions. A simplified form of the dynamical method produces, in the steady state in the weak-coupling limit, effective self-energies analogous to those in the Born approximation due to electron-phonon coupling. The two methods are then compared numerically on a resonant system consisting of a linear trimer weakly embedded between metal electrodes. This system exhibits an enhanced heating at high biases and long phonon equilibration times. Despite the differences in their formulation, the static and dynamical methods capture local current-induced heating and inelastic corrections to the current with good agreement over a wide range of conditions, except in the limit of very high vibrational excitations where differences begin to emerge.

Correlated electron-ion dynamics in metallic systems

In this paper we briefly discuss the problem of simulating non-adiabatic processes in systems that are usefully modelled using molecular dynamics. In particular we address the problems associated with metals, and describe two methods that can be applied: the Ehrenfest approximation and correlated electron-ion dynamics (CEID). The Ehrenfest approximation is used to successfully describe the friction force experienced by an energetic particle passing through a crystal, but is unable to describe the heating of a wire by an electric current. CEID restores the proper heating.

On the alignment of debris disks and their host stars' rotation axis -implications for spin-orbit misalignment in exoplanetary systems

It has been widely thought that measuring the misalignment angle between the orbital plane of a transiting exoplanet and the spin of its host star was a good discriminator between different migration processes for hot-Jupiters. Specifically, well-aligned hot-Jupiter systems (as measured by the Rossiter-McLaughlin effect) were thought to have formed via migration through interaction with a viscous disc, while misaligned systems were thought to have undergone a more violent dynamical history. These conclusions were based on the assumption that the planet-forming disc was well-aligned with the host star. Recent work by Lai et al. has challenged this assumption, and proposes that the star-disc interaction in the pre-main sequence phase can exert a torque on the star and change its rotation axis angle. We have estimated the stellar rotation axis of a sample of stars which host spatially resolved debris disks. Comparison of our derived stellar rotation axis inclination angles with the geometrically measured debris-disk inclinations shows no evidence for a misalignment between the two.

Thermal and quantum fluctuations in chains of ultracold polar molecules

Ultracold polar molecules, in highly anisotropic traps and interacting via a repulsive dipolar potential, may form one-dimensional chains at high densities. According to classical theory, at low temperatures there exists a critical value of the density at which a second-order phase transition from a linear to a zigzag chain occurs. We study the effect of thermal and quantum fluctuations on these self-organized structures using classical and quantum Monte Carlo methods, by means of which we evaluate the pair correlation function and the static structure factor. Depending on the parameters, these functions exhibit properties typical of a crystalline or of a liquid system. We compare the thermal and the quantum results, identifying analogies and differences. Finally, we discuss experimental parameter regimes where the effects of quantum fluctuations on the linear-zigzag transition can be observed.

Optimal control of atom transport for quantum gates in optical lattices

By means of optimal control techniques we model and optimize the manipulation of the external quantum state (center-of-mass motion) of atoms trapped in adjustable optical potentials. We consider in detail the cases of both noninteracting and interacting atoms moving between neighboring sites in a lattice of a double-well optical potentials. Such a lattice can perform interaction-mediated entanglement of atom pairs and can realize two-qubit quantum gates. The optimized control sequences for the optical potential allow transport faster and with significantly larger fidelity than is possible with processes based on adiabatic transport.