On the generation of metal clusters with the electrochemical scanning tunneling microscope

In the present work we consider two aspects of the deposition of metal clusters on an electrode surface. The formation of such clusters with the tip of a scanning tunneling microscope is simulated by atom dynamics. Subsequently the stability of these clusters is investigated by Monte Carlo simulations in a grand-canonical ensemble. In particular, the following systems were considered explicitly: Pd clusters on Au(111), Cu on Au(111), Ag on Au(111), Pb on Au(111) and Cu on Ag(111). The analysis of the results obtained for the different systems leads to the conclusion that optimal systems for nanostructuring are those where the metals participating have similar cohesive energies and negative heats of alloy formation. In this respect, the system Cu-Pd(111) is predicted as a good candidate for the formation of stable clusters. (c) 2005 Elsevier B.V. All rights reserved.

Boron in copper: A perfect misfit in the bulk and cohesion enhancer at a grain boundary

Using first principles electronic structure methods, we calculate the effects of boron impurities in bulk copper and at surfaces and grain boundaries. We find that boron segregation to the Sigma5(310)[001] grain boundary should strengthen the boundary up to 1.5 ML coverage (15.24 at./nm2). The maximal effect is observed at 0.5 ML and corresponds to boron atoms filling exclusively grain boundary interstices. In copper bulk, B causes significant distortion both in interstitial and regular lattice sites, for which boron atoms are either too big or too small. The distortion is compensated to a large extent when the interstitial and substitutional boron combine together to form a strongly bound dumbbell. Our prediction is that bound boron impurities should appear in a sizable proportion if not dominate in most experimental conditions. A large discrepancy between calculated heats of solution and experimental terminal solubility of B in Cu is found, indicating either a significant failure of the density functional approach or, more likely, strongly overestimated solubility limits in the existing B-Cu phase diagram.

The UMIST database for astrochemistry 1999

We report a new version of the UMIST database for astrochemistry. The previous (1995) version has been updated and its format has been revised. The database contains the rate coefficients, temperature ranges and - where available - the temperature dependence of 4113 gas-phase reactions important in astrophysical environments. The data involve 396 species and 12 elements. We have also tabulated permanent electric dipole moments of the neutral species and heats of formation. A new table lists the photo process cross sections (ionisation, dissociation, fragmentation) for a few species for which these quantities have been measured. Data for Deuterium fractionation are given in a separate table. Finally, a new online Java applet for data extraction has been created and its use is explained in detail. The detailed new datafiles and associated software are available on the World Wide Web at http://www.rate99.co.uk.

Combustible ionic liquids by design: is laboratory safety another ionic liquid myth?

The non-flammability of ionic liquids (ILs) is often highlighted as a safety advantage of ILs over volatile organic compounds (VOCs), but the fact that many ILs are not flammable themselves does not mean that they are safe to use near fire and/or heat sources; a large group of ILs ( including commercially available ILs) are combustible due to the nature of their positive heats of formation, oxygen content, and decomposition products.

Turning solid aluminium transparent by intense soft X-ray photoionization

Saturable absorption is a phenomenon readily seen in the optical and infrared wavelengths. It has never been observed in core-electron transitions owing to the short lifetime of the excited states involved and the high intensities of the soft X-rays needed. We report saturable absorption of an L-shell transition in aluminium using record intensities over 10(16)W cm(-2) at a photon energy of 92 eV. From a consideration of the relevant timescales, we infer that immediately after the X-rays have passed, the sample is in an exotic state where all of the aluminium atoms have an L-shell hole, and the valence band has approximately a 9 eV temperature, whereas the atoms are still on their crystallographic positions. Subsequently, Auger decay heats the material to the warm dense matter regime, at around 25 eV temperatures. The method is an ideal candidate to study homogeneous warm dense matter, highly relevant to planetary science, astrophysics and inertial confinement fusion.

The UMIST database for astrochemistry 1995

We report the release of a new version of the UMIST database for astrochemistry. The database contains the rate coefficients of 3864 gas-phase reactions important in interstellar and circumstellar chemistry and involves 395 species and 12 elements. The previous (1990) version of this database has been widely used by modellers. In addition to the rate coefficients, we also tabulate permanent electric dipole moments of the neutral species and heats of formation. A numerical model of the chemical evolution of a dark cloud is calculated and important differences to that calculated with the previous database noted.

A STUDY OF CARBON-MONOXIDE AND NEUTRAL CARBON IN THE S106 MOLECULAR CORE

Maps are presented of J=2-1 and J=3-2 (CO)-O-18 emission from the molecular environment of the bipolar nebula S106, together with complementary observations of the P-3(1)-P-3(0), C I emission. Line splitting observed extensively over the E molecular cloud suggests that it is best explained as the expanding remnant of a thick toroid surrounding the optical lobes. The poor correlation between the observed molecular line emission and dust continuum emission in the E cloud is probably due to a large temperature gradient. Strong C I emission from the protostellar candidate S106 FIR suggests the nearby presence of a powerful source of far-UV radiation, whose energy supply is unlikely to arise from gravitational contraction of a protostar. It is probable that this source is the star S106 LR, which also heats S106 FIR. There is evidence, in both C I and (CO)-O-18, for a predominantly blueshifted outflow from S106 IR, best interpreted as a stellar wind-driven shock into the toroidal remnant. (CO)-O-18 and (CO)-C-13 appear to be depleted, relative to canonical values for their abundances, in S106 FIR, despite its high optical extinction, which should discourage selective photodissociation. Elsewhere in the cloud the C I line profiles show a resemblance to those of (CO)-O-18, with intensity equivalent to a few photodissociation regions (PDRs) along the line of sight.

Observation of high transient gain in the germanium x-ray laser at 19.6 nm

The transient-excitation pumping scheme, in which a picosecond duration pulse rapidly heats the plasma preformed by a low-intensity nanosecond pulse, was used to pump the Ne-like germanium, J = 0-1 transition at 19.6 nm. A small-signal gain coefficient of 30 cm(-1) was measured for targets less than or equal to 5 mm long. (C) 1998 Optical Society of America.

Parametric study of non-relativistic electrostatic shocks and the structure of their transition layer

Nonrelativistic electrostatic unmagnetized shocks are frequently observed in laboratory plasmas and they are likely to exist in astrophysical plasmas. Their maximum speed, expressed in units of the ion acoustic speed far upstream of the shock, depends only on the electron-to-ion temperature ratio if binary collisions are absent. The formation and evolution of such shocks is examined here for a wide range of shock speeds with particle-in-cell simulations. The initial temperatures of the electrons and the 400 times heavier ions are equal. Shocks form on electron time scales at Mach numbers between 1.7 and 2.2. Shocks with Mach numbers up to 2.5 form after tens of inverse ion plasma frequencies. The density of the shock-reflected ion beam increases and the number of ions crossing the shock thus decreases with an increasing Mach number, causing a slower expansion of the downstream region in its rest frame. The interval occupied by this ion beam is on a positive potential relative to the far upstream. This potential pre-heats the electrons ahead of the shock even in the absence of beam instabilities and decouples the electron temperature in the foreshock ahead of the shock from the one in the far upstream plasma. The effective Mach number of the shock is reduced by this electron heating. This effect can potentially stabilize nonrelativistic electrostatic shocks moving as fast as supernova remnant shocks. 

Site symmetry dependence of repulsive interactions between chemisorbed oxygen atoms on Pt{100}-(1x1)

Ab initio total energy calculations using density functional theory with the generalized gradient approximation have been performed for the chemisorption of oxygen atoms on a Pt{100}-(1 x 1) slab. Binding energies for the adsorption of oxygen on different high-symmetry sites are presented. The bridge site is the most stable at a coverage of 0.5 ML, followed by the fourfold hollow site. The atop site is the least stable. This finding is rationalized by analyzing the ''local structures'' formed upon oxygen chemisorption. The binding energies and heats of adsorption at different oxygen coverages show that pairwise repulsive interactions are considerably stronger between oxygen atoms occupying fourfold sites than those occupying bridge sites. Analysis of the partial charge densities associated with Bloch states demonstrates that the O-Pt bond is considerably more localized at the bridge site. These effects cause a sharp drop in the heats of adsorption for oxygen on hollow sites when the coverage is increased from 0.25 to 0.5 ML. Mixing between oxygen p orbitals and Pt d orbitals can be observed over the whole metal d-band energy range.

Shape stabilised phase change materials based on a high melt viscosity HDPE and paraffin waxes

Shape stabilised phase change materials (SSPCMs) based on a high density poly(ethylene)(hv-HDPE) with high (H-PW, Tm = 56–58 °C) and low (L-PW, Tm = 18–23 °C) melting point paraffin waxes were readily prepared using twin-screw extrusion. The thermo-physical properties of these materials were assessed using a combination of techniques and their suitability for latent heat thermal energy storage (LHTES) assessed. The melt processing temperature (160 °C) of the HDPE used was well below the onset of thermal decomposition of H-PW (220 °C), but above that for L-PW (130 °C), although the decomposition process extended over a range of 120 °C and the residence time of L-PW in the extruder was <30 s. The SSPCMs prepared had latent heats up to 89 J/g and the enthalpy values for H-PW in the respective blends decreased with increasing H-PW loading, as a consequence of co-crystallisation of H-PW and hv-HDPE. Static and dynamic mechanical analysis confirmed both waxes have a plasticisation effect on this HDPE. Irrespective of the mode of deformation (tension, flexural, compression) modulus and stress decreased with increased wax loading in the blend, but the H-PW blends were mechanically superior to those with L-PW.

Numerical Analysis on a Dual-Loop Waste Heat Recovery System Coupled with an ORC for Vehicle Applications

The internal combustion (IC) engines exploits only about 30% of the chemical energy ejected through combustion, whereas the remaining part is rejected by means of cooling system and exhausted gas. Nowadays, a major global concern is finding sustainable solutions for better fuel economy which in turn results in a decrease of carbon dioxide (CO2) emissions. The Waste Heat Recovery (WHR) is one of the most promising techniques to increase the overall efficiency of a vehicle system, allowing the recovery of the heat rejected by the exhaust and cooling systems. In this context, Organic Rankine Cycles (ORCs) are widely recognized as a potential technology to exploit the heat rejected by engines to produce electricity. The aim of the present paper is to investigate a WHR system, designed to collect both coolant and exhausted gas heats, coupled with an ORC cycle for vehicle applications. In particular, a coolant heat exchanger (CLT) allows the heat exchange between the water coolant and the ORC working fluid, whereas the exhausted gas heat is recovered by using a secondary circuit with diathermic oil. By using an in-house numerical model, a wide range of working conditions and ORC design parameters are investigated. In particular, the analyses are focused on the regenerator location inside the ORC circuits. Five organic fluids, working in both subcritical and supercritical conditions, have been selected in order to detect the most suitable configuration in terms of energy and exergy efficiencies.

Three-dimensional simulations of gravitationally confined detonations compared to observations of SN 1991T

The gravitationally confined detonation (GCD) model has been proposed as a possible explosion mechanism for Type Ia supernovae in the single-degenerate evolution channel. It starts with ignition of a deflagration in a single off-centre bubble in a near-Chandrasekhar-mass white dwarf. Driven by buoyancy, the deflagration flame rises in a narrow cone towards the surface. For the most part, the main component of the flow of the expanding ashes remains radial, but upon reaching the outer, low-pressure layers of the white dwarf, an additional lateral component develops. This causes the deflagration ashes to converge again at the opposite side, where the compression heats fuel and a detonation may be launched. We first performed five three-dimensional hydrodynamic simulations of the deflagration phase in 1.4 M⊙ carbon/oxygen white dwarfs at intermediate-resolution (2563computational zones). We confirm that the closer the initial deflagration is ignited to the centre, the slower the buoyant rise and the longer the deflagration ashes takes to break out and close in on the opposite pole to collide. To test the GCD explosion model, we then performed a high-resolution (5123 computational zones) simulation for a model with an ignition spot offset near the upper limit of what is still justifiable, 200 km. This high-resolution simulation met our deliberately optimistic detonation criteria, and we initiated a detonation. The detonation burned through the white dwarf and led to its complete disruption. For this model, we determined detailed nucleosynthetic yields by post-processing 106 tracer particles with a 384 nuclide reaction network, and we present multi-band light curves and time-dependent optical spectra. We find that our synthetic observables show a prominent viewing-angle sensitivity in ultraviolet and blue wavelength bands, which contradicts observed SNe Ia. The strong dependence on the viewing angle is caused by the asymmetric distribution of the deflagration ashes in the outer ejecta layers. Finally, we compared our model to SN 1991T. The overall flux level of the model is slightly too low, and the model predicts pre-maximum light spectral features due to Ca, S, and Si that are too strong. Furthermore, the model chemical abundance stratification qualitatively disagrees with recent abundance tomography results in two key areas: our model lacks low-velocity stable Fe and instead has copious amounts of high-velocity 56Ni and stable Fe. We therefore do not find good agreement of the model with SN 1991T.