Reactivity of the Cu2O(1 0 0) surface: Insights from first principles calculations

We present a summary of results of systematic first principles calculations of the electronic and geometric structures of the Cu₂O(1 0 0) surface and the process of CO oxidation on this surface (energetics and pathways of adsorption, diffusion and reactions of CO and O₂ on the surface). The (p, T) phase diagram of the Cu₂O(1 0 0) in equilibrium of with gas phase O₂ built using the ab initio thermodynamics approach suggests that the O-terminated surface is preferred over the Cu-terminated one within the entire ranges of pressures and temperatures in which the compound exists. Metastable Cu-terminated Cu₂O(1 0 0) is found to undergo a surface reconstruction in agreement with experiment. We find CO to oxidize spontaneously on the O-terminated Cu₂O(1 0 0) surface by consuming surface O atoms. Our calculations also show that the surface O-vacancies left in the course of the CO oxidation can be easily filled with dissociative adsorption of the gas phase O₂ molecules, which are usually present in reaction environment.     

Improvement of the PLD process assisted by RF plasma for AlN growth

The pulsed-laser-deposition (PLD) method is particularly well suited for the growth of oxide thin films, but in the case of other compounds, such as nitrides, PLD presents some limitations which are mainly due to the low reactivity of nitrogen in comparison with oxygen. A possible way to overcome this problem is to increase the reactivity of the constituent species, via plasma assisted-pulsed-laser deposition. A plasma is coupled to the ablation chamber, in order to increase the density of reactive atomic species, which can be further incorporated in the growing film. This approach is described in this paper as well as the nature, energy, and concentration of the atomic and molecular species in the plasma as determined by various plasma diagnostics. These results are correlated to the growth of thin films in the particular case of the aluminum nitride compound. The composition and structure of the films are studied as a function of the growth conditions, and the positive effects of the additional discharge are evidenced on the film purity and properties. The fundamental problem with the PLD technique, especially with metallic targets, is the production of unwanted droplets that significantly worsen the properties of the films. To eliminate these droplets, a thin film has been grown with an experimental setup using two targets and crossed laser beams which gave positive results. PACS 81.15.Fg; 52.80.Pi; 77.84.Bw     

Detection

This review on second- and third-generation multidetectors devoted to heavy-ion collisions aims to cover the last twenty years. The presented list of devices is not exhaustive but regroups most of the techniques used during this period for nuclear reactions at intermediate energy (≃ 10A MeV to 1A GeV), both for charged-particle and neutron detection. The main part will be devoted to 4π multidetectors, projectile decay fragmentation, high-resolution magnetic spectrometers, auxiliary detectors and neutron detection. The last part will present the progress in electronics and detection in view of the construction of future-generation detectors.     

Synthesis and characterization of hollow ��-Fe2O3 sub-micron spheres prepared by sol�Cgel

In this work we report the preparation of magnetic hematite hollow sub-micron spheres (??-Fe₂O₃) by colloidal suspensions of ferric nitrate nine-hydrate (Fe(NO₃)₃·9H₂O) particles in citric acid solution by following the sol?Cgel method. After the gel formation, the samples were annealed at different temperatures in an oxidizing atmosphere. Annealing at 180°C resulted in an amorphous phase, without iron oxide formation. Annealing at 250°C resulted in coexisting phases of hematite, maghemite and magnetite, whereas at 400°C, only hematite and maghemite were found. Pure hematite hollow sub-micron spheres with porous shells were formed after annealing at 600°C. The characterization was performed by X-ray diffraction (XRD), Mössbauer spectroscopy (MS) and scanning electron microscopy (SEM).     

Relaxation of photoexcited Na$_\mathsf{3}$F

This paper describes the spectroscopy of Na₃F both in the frequency and time domains. The photoionization efficiency curve shows two thresholds, associated to two isomers. The excited electronic states of the C_2v isomer have been probed by photodepletion spectroscopy, and the results are used to analyze a time-resolved study of photoexcited Na₃F, probed by photoionization. The pump-probe signal clearly shows damped oscillations, the period of which is fitted to fs, close to twice the previously measured bending mode of Na₂F [1], while the relaxation time is fs.Received: 31 October 2003, Published online: 6 January 2004PACS: 36.40.Qv Stability and fragmentation of clusters - 33.50.-j Fluorescence and phosphorescence; radiationless transitions, quenching (intersystem crossing, internal conversion)     

Hopf bifurcation control via a dynamic state-feedback control

To relocate two Hopf bifurcation points, simultaneously, to any desired locations in n-dimensional nonlinear systems, a novel dynamic state-feedback control law is proposed. Analytical schemes to determine the control gains according to the conditions for the emergence of Hopf bifurcation are derived. To verify the effectiveness of the proposed control law, numerical examples are provided.     

Ultra-fast grain boundary diffusion and its contribution to surface segregation on a martensitic steel. Experiments and modeling

Phosphorus surface segregation was measured by Auger Electron Spectroscopy on a 17-4 PH martensitic stainless steel at 450, 550 and 600 °C. Surface segregation was shown to be much faster than expected which was attributed to a high contribution of phosphorus diffusion along the former austenitic grain boundaries. A model of surface segregation was developed following the Darken–du Plessis approach and taking account of both bulk and grain boundary solute diffusion. The phosphorus grain boundary diffusion coefficient in 17-4 PH was estimated: D_GB^< = 6.2 10⁴ exp(? 157 kJ mol^? 1/RT)cm² s^? 1. It is found to be more than three orders of magnitude higher in 17-4 PH steel than in α-iron.     

Dynamics of molybdenum nano structure formation on the TiO2(1 1 0) surface: A kinetic Monte Carlo approach

The rutile TiO₂(1 1 0) surface is a highly anisotropic surface exhibiting “channels” delimited by oxygen rows. In previous experimental and theoretical DFT works we could identify the molybdenum adsorption sites. They are located inside the channels. Moreover, experimental studies have shown that during subsequent annealing after deposition, special molybdenum nano structures can be formed, especially two monolayer high pyramidal chains of atoms.In order to better understand the dynamics of nano structure formation, we present a kinetic Monte Carlo study on diffusion and adsorption of molybdenum atoms on a TiO₂(1 1 0) surface. A quasi one-dimensional lattice gas model has been used which describes the possible adsorption sites of a Mo atom in a single channel of the surface. The atomic positions of a 1.5 monolayer thick Mo film formed of pyramidal chains define the lattice sites of the model. Thereby the formation of three-dimensional clusters could be studied. Here we have studied the cluster formation as a function of parameters that can be controlled in a growth experiment by physical vapor deposition: deposition and annealing temperature, flux and total amount of deposited Mo. Good qualitative agreement with recent experiments is obtained.     

Temperature dependence of the absorption spectrum of CH4 by high resolution spectroscopy at 81 K: (I) The region of the 2ν3 band at 1.66 μm

In a recent contribution, (Gao B, Kassi S, Campargue A. Empirical low energy values for methane transitions in the 5852-6181 cm⁻¹ region by absorption spectroscopy at 81 K. J Mol Spectrosc 2009;253:55-63.), the low energy values of methane transitions between 1.71 and 1.62 μm were derived from the variation of the line intensities between 296 and 81 K. The line intensities at 81 K were retrieved from the high resolution absorption spectrum of methane recorded at liquid nitrogen temperature by direct absorption spectroscopy using a cryogenic cell and a series of distributed feed back (DFB) diode lasers. For the line intensities at 296 K, the values provided by the HITRAN database were used. As a consequence of the relatively high intensity cut off (4×10⁻²⁴ cm/molecule) of the HITRAN line list in the considered region, the lower energy values were derived for only 845 of the 2187 transitions measured at 81 K. In the present work, our line list was extended by the retrieval of many weak line intensities leading to a set of 3251 transitions. The minimum value of the measured line intensities (at 81 K) is on the order of 10⁻²⁶ cm/molecule. In relation with the project “Greenhouse Gases Observing Satellite” (GOSAT), a much more complete line list for CH₄ at 296 K has become available (intensity cut off of 4×10⁻²⁶ cm/molecule). By applying the two temperature method to our line intensities at 81 K and GOSAT intensities at 296 K, the lower energy values of 2297 transitions could be derived. These transitions represent 99.1% and 90.8% of the total absorbance in the region, at 81 and 296 K respectively. This line list provided as Supplementary Material allows then accounting for the temperature dependence of CH₄ absorption below 300 K. The investigated spectral range is dominated by the 2ν₃ band near 6005 cm⁻¹ which is of particular interest for atmospheric retrievals. The factor 2 narrowing of the Doppler linewidth from room temperature down to 81 K has allowed the resolution of a number of 2ν₃ multiplets and improving the line intensity retrievals. A detailed comparison with GOSAT and HITRAN line lists has revealed a number of possible improvements.