Chemisorption of atomic aluminum on Si(111): Evidence for an adsorbate-induced relaxation based on ab initio cluster-model calculations

Interaction models of atomic Al with Si4H9, Si4H7, and Si6H9 clusters have been studied to simulate Al chemisorption on the Si(111) surface in the atop, fourfold atop, and open sites. Calculations were carried out using nonempirical pseudopotentials in the framework of the ab initio Hartree-Fock procedure. Equilibrium bond distances, binding energies for adsorption, and vibrational frequencies of the adatoms are calculated. Several basis sets were used in order to show the importance of polarization effects, especially in the binding energies. Final results show the importance of considering adatom-induced relaxation effects to specify the order of energy stabilities for the three different sites, the fourfold atop site being the preferred one, in agreement with experimental findings.

Ab initio cluster-model study of the on-top chemisorption of F and Cl on Si(111) and Ge(111) surfaces

The interaction of atomic F and Cl with Si4H9 and Ge4H9 cluster models has been studied by using ab initio pseudopotentials and basis sets of increasing complexity. The results show that the effect of d orbitals is important in order to reproduce the experimental findings. However, the use of polarization functions in the atoms which are directly involved in the chemisorption bond leads to results which are very close to those obtained using extended basis sets. The local nature of the chemisorption bond is also interpreted by means of a Mulliken population analysis. For F-Si4H9 and Cl-Si4H9 the present results are in good agreement with previous ab initio all-electron calculations, and for the chemisorption of Cl on Si(111) and Ge(111) surfaces, good agreement is found with respect to the available experimental results as well as with previous slab calculations based on the local-density-functional formalism.

X-ray diffraction, thermal analysis, and Raman scattering study of K2BeF4 and comparation to other member of the (beta)-K2SO4 family with ferroelectric -paraelectric transition

Thermal analysis, powder diffraction, and Raman scattering as a function of the temperature were carried out on K2BeF4. Moreover, the crystal structure was determined at 293 K from powder diffraction. The compound shows a transition from Pna21 to Pnam space group at 921 K with a transition enthalpy of 5 kJ/mol. The transition is assumed to be first order because the compound shows metastability. Structurally and spectroscopically the transition is similar to those observed in (NH4)2SO4, which suggests that the low-temperature phase is ferroelectric. In order to confirm it, the spontaneous polarization has been computed using an ionic model.

Catalan beauty and the transnational beast: Barcelona on screen

This article explores the case of Barcelona as paradigmatic global city in such transnational productions as Vicky Cristina Barcelona by Woody Allen (2008) and Biutiful by Alejandro González Iñárritu (2010). Allen"s film shows the extreme dilution that national and linguistic identity undergoes under foreign eyes in its rendition of a"hip Barcelona" for tourists"invaded" by transnational subjects in search of bourgeois pleasures. Maybe in pursuit of a more"real" city, Iñárritu"s Biutiful moves to the Barcelona of the immigrants and the undocumented, a transnational and paradoxical location inhabited by those who need to cross borders in order to survive. Through reference to the work of Manuel Castells, Saskia Sassen, Neil Smith and Michel De Certeau among others, we argue that neither of these representations of the city is more real or unreal than the other. In their drastically divergent ways, both films contribute their external perspectives to the imaginary construction of Barcelona as a fascinating global city and can be seen as a dyptich of a transnational Barcelona. Further, they contribute to the ongoing debate about the polarization between the local and the global, the construction of urban boarders inside cities through gentrification, the transformation of the places we (would like to) inhabit, and the translation of all these into visual terms.

Simple holographic polarogram

A new technique capable of obtaining quantitative values of the rotation angle of the polarization vector by using holography is presented. This is a two-stage holographic process; during the recording stage a hologram of the object of interest is obtained. The reference beam is composed of two beams that form a small angle between them and keep their polarization states at right angles to each other. In the reconstruction stage of the hologram, two images from the hologram are obtained along two different angles. As a result of the interference between these two images, a set of parallel fringes is formed at the image plane. The fringe contrast on the reconstruction is related to the angle of the polarization vector of the light at each position on the image plane. Measurements of the rotation of the polarization angle of a fraction of a degree were obtained. The main application of this technique is in the study of transient phenomena, where single-shot measurements are the only means of obtaining reliable data.

Contribution of S6K1/MAPK signaling pathways in the response to oxidative stress: activation of RSK and MSK by hydrogen peroxide

Cells respond to different kind of stress through the coordinated activation of signaling pathways such as MAPK or p53. To find which molecular mechanisms are involved, we need to understand their cell adaptation. The ribosomal protein, S6 kinase 1 (S6K1), is a common downstream target of signaling by hormonal or nutritional stress. Here, we investigated the initial contribution of S6K1/MAPK signaling pathways in the cell response to oxidative stress produced by hydrogen peroxide (H2O2). To analyze S6K1 activation, we used the commercial anti-phospho-Thr389-S6K1 antibody most frequently mentioned in the bibliography. We found that this antibody detected an 80-90 kDa protein that was rapidly phosphorylated in response to H2O2 in several human cells. Unexpectedly, this phosphorylation was insensitive to both mTOR and PI3K inhibitors, and knock-down experiments showed that this protein was not S6K1. RSK and MSK proteins were candidate targets of this phosphorylation. We demonstrated that H2O2 stimulated phosphorylation of RSK and MSK kinases at residues that are homologous to Thr389 in S6K1. This phosphorylation required the activity of either p38 or ERK MAP kinases. Kinase assays showed activation of RSK and MSK by H2O2. Experiments with mouse embryonic fibroblasts from p38 animals" knockout confirmed these observations. Altogether, these findings show that the S6K1 signaling pathway is not activated under these conditions, clarify previous observations probably misinterpreted by non-specific detection of proteins RSK and MSK by the anti-phospho-Thr389-S6K1 antibody, and demonstrate the specific activation of MAPK signaling pathways through ERK/p38/RSK/MSK by H2O2.

Nonperturbative semiclassical stability of de Sitter spacetime for small metric deviations

We consider the linearized semiclassical Einstein equations for small deviations around de Sitter spacetime including the vacuum polarization effects of conformal fields. Employing the method of order reduction, we find the exact solutions for general metric perturbations (of scalar, vector and tensor type). Our exact (nonperturbative) solutions show clearly that in this case de Sitter is stable with respect to small metric deviations and a late-time attractor. Furthermore, they also reveal a breakdown of perturbative solutions for a sufficiently long evolution inside the horizon. Our results are valid for any conformal theory, even self-interacting ones with arbitrarily strong coupling.

Diradicals acting through diamagnetic phenylene vinylene bridges: Raman spectroscopy as a probe to characterize spin delocalization

We present a complete Raman spectroscopic study in two structurally well-defined diradical species of different lengths incorporating oligo p-phenylene vinylene bridges between two polychlorinated triphenylmethyl radical units, a disposition that allows sizeable conjugation between the two radicals through and with the bridge. The spectroscopic data are interpreted and supported by quantum chemical calculations. We focus the attention on the Raman frequency changes, interpretable in terms of: (i) bridge length (conjugation length); (ii) bridge conformational structure; and (iii) electronic coupling between the terminal radical units with the bridge and through the bridge, which could delineate through-bond spin polarization, or spin delocalization. These items are addressed by using the"oligomer approach" in conjunction with pressure and temperature dependent Raman spectroscopic data. In summary, we have attempted to translate the well-known strategy to study the electron (charge) structure of π−conjugated molecules by Raman spectroscopy to the case of electron (spin) interactions via the spin delocalization mechanism.

Electrical pump & probe and injected carrier losses quantification in Er doped Si slot waveguides

Electrically driven Er3+ doped Si slot waveguides emitting at 1530 nm are demonstrated. Two different Er3+ doped active layers were fabricated in the slot region: a pure SiO2 and a Si-rich oxide. Pulsed polarization driving of the waveguides was used to characterize the time response of the electroluminescence (EL) and of the signal probe transmission in 1 mm long waveguides. Injected carrier absorption losses modulate the EL signal and, since the carrier lifetime is much smaller than that of Er3+ ions, a sharp EL peak was observed when the polarization was switched off. A time-resolved electrical pump & probe measurement in combination with lock-in amplifier techniques allowed to quantify the injected carrier absorption losses. We found an extinction ratio of 6 dB, passive propagation losses of about 4 dB/mm, and a spectral bandwidth > 25 nm at an effective d.c. power consumption of 120 μW. All these performances suggest the usage of these devices as electro-optical modulators.

Spectroscopic ellipsometry study of the In1-x Gax Asy P1-y / InP Heterojunctions grown by metalorganic chemical-vapor deposition

The dielectric functions of InP, In0.53Ga0.47As, and In0.75Ga0.25As0.5P0.5 epitaxial layers have been measured using a polarization modulation spectroscopic ellipsometer in the 1.5 to 5.3 eV region. The oxide removal procedure has been carefully checked by comparing spectroscopic ellipsometry and x ray photoelectron spectroscopy measurements. These reference data have been used to investigate the structural nature of metalorganic chemical vapor deposition grown In0.53Ga0.47As/InP and In0.75Ga0.25As0.5P0.5/InP heterojunctions, currently used for photodiodes and laser diodes. The sharpness of the interfaces has been systematically compared for the two types of heterojunctions: In1 xGaxAsy/InP and InP/In1 xGaxAsyP1 y. The sharpest interface is obtained for InP growth on In0.75Ga0.25As0.5P0.5 where the interface region is estimated to be (10±10) Å thick. The importance of performing in situ SE measurements is emphasized.

Highly textured Sr, Nb, co-doped BiFeO3 thin films grown on SrRuO3/Si substrates by rf-sputtering

In this study, (011)-highly oriented Sr, Nb co-doped BiFeO3 (BFO) thin films were successfully grown on SrRuO3/Si substrates by rf-magnetron sputtering. The presence of parasite magnetic phases was ruled out based on the high resolution x-ray diffraction data. BFO films exhibited a columnar-like grain growth with rms surface roughness values of 5.3 nm and average grain sizes of 65-70 nm for samples with different thicknesses. Remanent polarization values (2Pr) of 54 lC cm 2 at room temperature were found for the BFO films with a ferroelectric behavior characteristic of an asymmetric device structure. Analysis of the leakage mechanisms for this structure in negative bias suggests Schottky injection and a dominant Poole-Frenkel trap-limited conduction at room temperature. Oxygen vacancies and Fe3þ/Fe2þ trap centers are consistent with the surface chemical bonding states analysis from x-ray photoelectron spectroscopy data. The (011)-BFO/ SrRuO3/Si film structure exhibits a strong magnetic interaction at the interface between the multiferroic film and the substrate layer where an enhanced ferromagnetic response at 5 K was observed. Zero-field cooled (ZFC) and field cooled (FC) magnetization curves of this film system revealed a possible spin glass behavior at spin freezing temperatures below 30 K depending on the BFO film thickness.

1.48 and 1.84 µm thulium emissions in monoclinic KGd(WO4)2 single crystals

By exciting at 788 nm, we have characterized the near infrared emissions of trivalent thulium ions in monoclinic KGd(WO4)2 single crystals at 1.48 and 1.84 mm as a function of dopant concentration from 0.1% to 10% and temperature from 10 K to room temperature. We used the reciprocity method to calculate the maximum emission cross-section of 3.0310220 cm2 at 1.838 mm for the polarization parallel to the Nm principal optical direction. These results agrees well with the experimental data. Experimental decay times of the 3H4!3F4 and 3F4!3H6 transitions have been measured as a function of thulium concentration.

Correlation of the EPR properties of perchlorotriphenylmethyl radical and their efficiency as DNP polarizers

Water soluble perchlorinated trityl (PTM) radicals were found to be effective 95 GHz DNP (dynamic nuclear polarization) polarizers in ex situ (dissolution) 13C DNP (Gabellieri et al., Angew Chem., Int. Ed. 2010, 49, 3360). The degree of the nuclear polarization obtained was reported to be dependent on the position of the chlorine substituents on the trityl skeleton. In addition, on the basis of the DNP frequency sweeps it was suggested that the 13C NMR signal enhancement is mediated by the Cl nuclei. To understand the DNP mechanism of the PTM radicals we have explored the 95 GHz EPR characteristics of these radicals that are relevant to their performance as DNP polarizers. The EPR spectra of the radicals revealed axially symmetric g-tensors. A comparison of the spectra with the 13C DNP frequency sweeps showed that although the solid effect mechanism is operational the DNP frequency sweeps reveal some extra width suggesting that contributions from EPR forbidden transitions involving 35,37Cl nuclear flips are likely. This was substantiated experimentally by ELDOR (electron-electron double resonance) detected NMR measurements, which map the EPR forbidden transitions, and ELDOR experiments that follow the depolarization of the electron spin upon irradiation of the forbidden EPR transitions. DFT (density functional theory) calculations helped to assign the observed transitions and provided the relevant spin Hamiltonian parameters. These results show that the 35,37Cl hyperfine and nuclear quadrupolar interactions cause a considerable nuclear state mixing at 95 GHz thus facilitating the polarization of the Cl nuclei upon microwave irradiation. Overlap of Cl nuclear frequencies and the 13C Larmor frequency further facilitates the polarization of the 13C nuclei by spin diffusion. Calculation of the 13C DNP frequency sweep based on the Cl nuclear polarization showed that it does lead to an increase in the width of the spectra, improving the agreement with the experimental sweeps, thus supporting the existence of a new heteronuclear assisted DNP mechanism.

Behavior of propagating and evanescent components in azimuthally polarized non-paraxial fields

The contribution of the propagating and the evanescent waves associated with freely propagating non-paraxial light fields whose transverse component is azimuthally polarized at some plane is investigated. Analytic expressions are derived for describing both the spatial shape and the relative weight of the propagating and the evanescent components integrated over the transverse plane. The analysis is carried out within the framework of the plane-wave angular spectrum approach. These results are used to illustrate the behavior of a kind of donut-like beams with transverse azimuthal polarization at some plane.

Large Magnetoresistance in Fe/MgO/FeCo(001) Epitaxial Tunnel-Junctions on GaAs(001).

We present tunneling experiments on Fe~001!/MgO~20 Å!/FeCo~001! single-crystal epitaxial junctions of high quality grown by sputtering and laser ablation. Tunnel magnetoresistance measurements give 60% at 30 K, to be compared with 13% obtained recently on ~001!-oriented Fe/amorphous-Al2O3 /FeCo tunnel junctions. This difference demonstrates that the spin polarization of tunneling electrons is not directly related to the density of states of the free metal surface Fe~001! in this case but depends on the actual electronic structure of the entire electrode/barrier system.