A quantitative determination of reaction mechanisms from density functional theory calculations: Fischer-Tropsch synthesis on flat and stepped cobalt surfaces

We systematically investigated the mechanism of the C-1 + C-1 coupling reactions using density functional theory. The activation energies of C-1 + C-1 coupling and carbon hydrogenation reactions on both flat and stepped surfaces were calculated and analyzed. Moreover, the coverages of adsorbed C-1 species were estimated, and the reaction rates of all possible C-1 + C-1 coupling pathways were quantitatively evaluated. The results suggest that the reactions of CH2 + CH2 and CH3 + C at steps are most likely to be the key C-1 + C-1 coupling steps in FT synthesis on Co catalysts. The reactions of C-2 + C-1 and C-3 + C-1 coupling also were studied; the results demonstrate that in addition to the pathways of RCH + CH2 and RCH2 + C, the coupling of RC + C and RC + CH also may contribute to the chain growth after C-1. (C) 2008 Elsevier Inc. All rights reserved.

A comparative electrochemical study of diffusion in room temperature ionic liquid solvents versus acetonitrile

Measurements on the diffusion coefficient of the neutral molecule N,N,N',N'-tetramethyl-para-phenylenediamine and the radical cation and dication generated by its one- and two-electron oxidation, respectively, are reported over the range 298-348 K in both acetonitrile and four room temperature ionic liquids (RTILs). Data were collected using single and double potential step chronamperometry at a gold disk electrode of micrometer dimension, and analysed via fitting to the appropriate analytical expression or, where necessary, to simulation. The variation of diffusion coefficient with temperature was found to occur in an Arrhenius-type manner for all combinations of solute and solvent. For a given ionic liquid, the diffusional activation energies of each species were not only closely equivalent to each other, but also to the RTIL's activation energy of viscous flow. In acetonitrile supported with 0.1 M tetrabutylammonium perchlorate, the ratio in diffusion coefficients of the radial cation and dication tot he neutral molecule were calculated as 0.89 +/- 0.05 and 0.51 +/- 0.03, respectively. In contrast, amongst the ionic liquids the same ratios were determined to be on average 0.53 +/- 0.04 and 0.33 +/- 0.03. The consequences of this dissimilarity are considered in terms of the modelling of voltammetric data gathered within ionic liquid solvents.

A density functional theory study of the a-olefin selectivity in Fischer-Tropsch synthesis

We studied the alpha-olefin selectivity in Fischer-Tropsch (FT) synthesis using density functional theory (131717) calculations. We calculated the relevant elementary steps from C-2 to C-6 species. Our results showed that the barriers of hydrogenation and dehydrogenation reactions were constant with different chain lengths, and the chemisorption energies of alpha-olefins from DFT calculations also were very similar, except for C-2 species. A simple expression of the paraffin/olefin ratio was obtained based on a kinetic model. Combining the expression of the paraffin/olefin ratio and our calculation results, experimental findings are satisfactorily explained. We found that the physical origin of the chain length dependence of paraffin/olefin ratio is the chain length dependence of both the van der Waals interaction between adsorbed alpha-olefins and metal surfaces and the entropy difference between adsorbed and gaseous alpha-olefins, and that the greater chemisorption energy of ethylene is the main reason for the abnormal ethane/ethylene ratio. (c) 2008 Elsevier Inc. All rights reserved.

A density functional theory study of carbon monoxide oxidation on the Cu3Pt(111) alloy surface: Comparison with the reactions on Pt(111) and Cu(111)

Alloying metals is often used as an effective way to enhance the reactivity of surfaces. Aiming to shed light on the effect of alloying on reaction mechanisms, we carry out a comparative study of CO oxidation on Cu3Pt(111), Pt(111), and Cu(111) by means of density functional theory calculations. Alloying effects on the bonding sites and bonding energies of adsorbates, and the reaction pathways are investigated. It is shown that CO preferentially adsorbs on an atop site of Pt and O preferentially adsorbs on a fcc hollow site of three Cu atoms on Cu3Pt(111). It is also found that the adsorption energies of CO (or O-a) decreases on Pt (or Cu) on the alloy surface with respect to those on pure metals. More importantly, having identified the transition states for CO oxidation on those three surfaces, we found an interesting trend for the reaction barrier on the three surfaces. Similar to the adsorption energies, the reaction barrier on Cu3Pt possesses an intermediate value of those on pure Pt and Cu metals. The physical origin of these results has been analyzed in detail. (C) 2001 American Institute of Physics.

Investigation of an electron string ion source with field emission cathode

The string mode of operation for an electron beam ion source uses axially oscillating electrons in order to reduce power consumption, also simplifying the construction by omitting the collector with cooling requirements and has been called electron string ion source (ESIS). We have started a project (supported by INTAS and GSI) to use Schottky field emitting cathode tips for generating the electron string. The emission from these specially conditioned tips is higher by orders of magnitude than the focused Brillouin current density at magnetic fields of some Tesla and electron energies of some keV. This may avoid the observed instabilities in the transition from axially oscillating electrons to the string state of the electron plasma, opening a much wider field of possible operating parameters for an ESIS. Besides the presentation of the basic features, we emphasize in this paper a method to avoid damaging of the field, emission tip by backstreaming ions. (C) 2008 American Institute of Physics.

Polarization studies of radiative electron capture into highly-charged uranium ions

Recent advances in the development of 2D microstrip detectors open up new possibilities for hard x-ray spectroscopy, in particular for polarization studies. These detectors make ideal Compton polarimeters, which enable us to study precisely the polarization of hard x-rays. Here, we present recent results from measurements of Radiative Electron Capture into the K-shell of highly-charged uranium ions. The experiments were performed with a novel 2D Si(Li) Compton polarimeter at the Experimental Storage Ring at GSI. Stored and cooled beams of U91+ and U92+ ions, with kinetic energies of 43 MeV/u and 96 MeV/u respectively, were crossed with a hydrogen gasjet. The preliminary data analysis shows x-rays from the K-REC process, emitted perpendicularly to the ion beam, to be strongly linearly polarized.

Measurements of the XUV transmission of aluminium with a soft x-ray laser

We have used XUV lasers to make absolute measurements of the photoabsorption coefficient of Al at energies just below that of the L3 absorption edge at 72.7 eV. Transmission measurements at photon energies of 53.7 and 63.3 eV have been made using Ne-like Ni and Ge XUV lasers. The XUV laser output was recorded in first and second orders using a flat-field spectrometer. Al foils with steps of various thicknesses were placed over the first order diffracted signal, while the second order diffraction was used to monitor the beam profile at each position. The transmission data agree extremely well with the original measurements at these wavelengths made by Henke and co-workers (Henke B L, Gullikson E M and Davis J C 1993 At. Data Nucl. Data Tables 54 18 1), but are in conflict with subsequent measurements which are currently in common use (Gullikson E M, Denham P, Mrowka S and Underwood J H 1994 Phys. Rev. B 49 16 283). The exact values of the absorption coefficients in this region of the spectrum have significant implications for the diagnosis of the energy and intensity output of XUV lasers.

Many-body theory calculations of positron binding to negative ions

A many-body theory approach developed by the authors [Phys. Rev. A 70, 032720 (2004)] is applied to positron bound states and annihilation rates in atomic systems. Within the formalism, full account of virtual positronium (Ps) formation is made by summing the electron-positron ladder diagram series, thus enabling the theory to include all important many-body correlation effects in the positron problem. Numerical calculations have been performed for positron bound states with the hydrogen and halogen negative ions, also known as Ps hydride and Ps halides. The Ps binding energies of 1.118, 2.718, 2.245, 1.873 and 1.393 eV and annihilation rates of 2.544, 2.482, 1.984, 1.913 and 1.809 ns^{-1}, have been obtained for PsH, PsF, PsCl, PsBr and PsI, respectively.

Effect of self-generated magnetic fields on fast-electron beam divergence in solid targets

The collimating effect of self-generated magnetic fields on fast-electron transport in solid aluminium targets irradiated by ultra-intense, picosecond laser pulses is investigated in this study. As the target thickness is varied in the range of 25 mu m to 1.4 mm, the maximum energies of protons accelerated from the rear surface are measured to infer changes in the fast-electron density and therefore the divergence of the fast-electron beam transported through the target. Purely ballistic spreading of the fast-electrons would result in a much faster decrease in the maximum proton energy with increasing target thickness than that measured. This implies that some degree of 'global' magnetic pinching of the fast-electrons occurs, particularly for thick (>400 mu m) targets. Numerical simulations of electron transport are in good agreement with the experimental data and show that the pinching effect of the magnetic field in thin targets is significantly reduced due to disruption of the field growth by refluxing fast-electrons.

Electronic structure and total energy of interstitial hydrogen in iron: Tight-binding models

An application of the tight binding approximation is presented for the description of electronic structure and interatomic force in magnetic iron, both pure and containing hydrogen impurities. We assess the simple canonical d-band description in comparison to a non orthogonal model including s and d bands. The transferability of our models is tested against known properties including the segregation energies of hydrogen to vacancies and to surfaces of iron. In many cases agreement is remarkably good, opening up the way to quantum mechanical atomistic simulation of the effects of hydrogen on mechanical properties.

Effect of batch size on mechanical properties of granules in high shear granulation

The flow patterns in a high shear granulator depend on the fill volume. For example, DEM simulations reported by Terashita et al. [1] show that fill volume affects the velocities and kinetic energies of the particles. It also influences the granule size distribution [2]. Here the effects on the properties of the granule are described. The total mass of the granulate material was varied without changing the other variables such as impeller speed, granulation time and liquid to solid ratio. The resulting mechanical properties, such as strength, yield stress and Young's modulus, of the granules were measured. For the materials studied in the current work, increasing the fill factor (batch size) increased the values of these material parameters. This could be explained by the relative increase in the number and intensity of collisions between the particles, when the size of a batch was increased, leading to smaller porosities. (c) 2010 Elsevier B.V. All rights reserved.

Generation and optimization of electron currents along the walls of a conical target for fast ignition

The interaction of an ultraintense laser pulse with a conical target is studied by means of numerical particle-in-cell simulations in the context of fast ignition. The divergence of the fast electron beam generated at the tip of the cone has been shown to be a crucial parameter for the efficient coupling of the ignition laser pulse to the precompressed fusion pellet. In this paper, we demonstrate that a focused hot electron beam is produced at the cone tip, provided that electron currents flowing along the surfaces of the cone sidewalls are efficiently generated. The influence of various interaction parameters over the formation of these wall currents is investigated. It is found that the strength of the electron flows is enhanced for high laser intensities, low density targets, and steep density gradients inside the cone. The hot electron energy distribution obeys a power law for energies of up to a few MeV, with the addition of a high-energy Maxwellian tail.

Electron-beam treatment of poly(lactic acid) to control degradation profiles

Bioresorbable polymers such as polylactide (PIA) and polylactide-co-glycolide (PLGA) have been used successfully as biomaterials in a wide range of medical applications. However, their slow degradation rates and propensity to lose strength before mass have caused problems. A central challenge for the development of these materials is the assurance of consistent and predictable in vivo degradation. Previous work has illustrated the potential to influence polymer degradation using electron beam (e-beam) radiation. The work addressed in this paper investigates further the utilisation of e-beam radiation in order to achieve a more surface specific effect. Variation of e-beam energy was studied as a means to control the effective penetrative depth in poly-L-lactide (PLEA). PLEA samples were exposed to e-beam radiation at individual energies of 0.5 MeV, 0.75 MeV and 1.5 MeV. The near-surface region of the PLEA samples was shown to be affected by e-beam irradiation with induced changes in molecular weight, morphology, flexural strength and degradation profile. Moreover, the depth to which the physical properties of the polymer were affected is dependent on the beam energy used. Computer modelling of the transmission of each e-beam energy level used corresponded well with these findings. (C) 2010 Elsevier Ltd. All rights reserved.

Prospective Evaluation of Clinical and Ultrasound Findings in Ankle Disease in Juvenile Idiopathic Arthritis: Importance of Ankle Ultrasound

Objective. To prospectively compare clinical examination of the ankle structures with ultrasound (US) findings. Methods. In 42 children with juvenile idiopathic arthritis (JIA; 25 girls, 17 boys, mean age 11.3 yrs, range 2.3–22.3 yrs), a total of 61 swollen/painful ankles were assessed clinically and ultrasonographically. Accurate clinical examination of the entire ankle joint was performed, focusing especially on 3 regions — tibiotalar joint and medial and lateral tendons. Clinical and US findings were both scored 0–3 (normal-severe). Results. US demonstrated no signs of tibiotalar joint effusion in 14 out of 43 ankles considered clinically involved. For the medial tendons, US showed tenosynovitis in 13 ankles out of 31 thought to be clinically normal; and for the lateral tendons, of the 19 deemed to be clinically involved, less than 50% had involvement on US. Very poor agreement was observed comparing the clinical and US scores for the 3 regions: tibiotalar joint, kappa = 0.3; medial tendons, kappa = 0.24; lateral tendons, kappa = 0.25. With regard to other ankle structures, only 39% of the subtalar (talocalcaneal) joints considered clinically involved were deemed abnormal on US. Finally, of the 10 ankles with talonavicular US effusion, only 2 were considered clinically involved. Conclusion. Using US findings as the “gold standard,” clinical examination of the ankle in children with JIA was found to be inadequate in identifying the structures involved. US assessment prior to any glucocorticoid injection should be considered to improve the outcome. A prospective study comparing the outcome following clinical- versus US-guided ankle joint injection should be undertaken, to confirm our findings.

Scaling of proton acceleration driven by petawatt-laser-plasma interactions

The possibility of using high-power lasers to generate high-quality beams of energetic ions is attracting large global interest. The prospect of using laser-accelerated protons in medicine attracts particular interest, as these schemes may lead to compact and relatively low-cost sources. Among the challenges remaining before these sources can be used in medicine is to increase the numbers and energies of the ions accelerated. Here, we extend the energy and intensity range over which proton scaling is experimentally investigated, up to 400 J and 6 x 10(20) W cm(-2) respectively, and find a slower proton scaling than previously predicted. With the aid of plasma-expansion simulation tools, our results suggest the importance of time-dependent and multidimensional effects in predicting the maximum proton energy in this ultrahigh-intensity regime. The implications of our new understanding of proton scaling for potential medical applications are discussed.