Evidence for oxygen-island formation on Al(111): Cluster-model theory and x-ray photoelectron spectroscopy

The O 1s x-ray photoelectron spectroscopy spectrum for Al(111)/O at 300 K shows two components whose behavior as a function of time and variation of detection angle are consistent with either (a) a surface species represented by the higher binding-energy (BE) component and a subsurface species represented by the lower BE component, or (b) small close-packed oxygen islands with the interior atoms represented by the lower BE component and the perimeter atoms by the higher BE component. We have modeled both situations using ab initio Hartree-Fock wave functions for clusters of Al and O atoms. For an O atom in a threefold site, it was found that a below-surface position gave a higher O 1s BE than an above-surface position, incompatible with interpretation (a). This change in the O 1s BE could arise because the bond for O to Al may have a more covalent character when the O is below the surface than when it is above the surface. We present evidence consistent with this view. An O adatom island with all the O atoms in threefold sites gives calculated O 1s BE's which are significantly higher for the perimeter O atoms. Further, the results for an isolated O island without the Al substrate present also give higher BE¿s for the perimeter atoms. Both these results are consistent with interpretation (b). Published scanning-tunneling-microscopy data supports the suggestion that the chemisorbed state consists of small, close-packed islands, whereas the presence of two vibrational modes in high-resolution electron-energy-loss spectroscopy data has been interpreted as representing surface and subsurface oxygen atoms. In light of the present results, we suggest that a vibrational interpretation in terms of interior and perimeter adatoms should be considered.

Assessing the pH and DP of canvasses with NIR spectroscopy

The canvas support in easel paintings is composed mainly of cellulose. One of the maindegradation paths of cellulose is acid-catalysed hydrolysis, which means that in an acidic environment (low pH), its degradation proceeds at a faster rate (Strlič et al., 2005).The main effect of acid-catalysed hydrolysis is the breaking up of the polymer chains,measured by the “Degree of Polymerisation” (DP). The lowering of the DP value impliesa lower mechanical strength of the textile (Scicolone, 1993), and thus this parameter canbe used to monitor degradation. Knowing these two parameters can, therefore, be veryinformative regarding the condition of the canvas support.

Polydispersity index from linear viscoelastic data: Unimodal and bimodal linear polymer melts

This article describes a method for determining the polydispersity index Ip2=Mz/Mw of the molecular weight distribution (MWD) of linear polymeric materials from linear viscoelastic data. The method uses the Mellin transform of the relaxation modulus of a simple molecular rheological model. One of the main features of this technique is that it enables interesting MWD information to be obtained directly from dynamic shear experiments. It is not necessary to achieve the relaxation spectrum, so the ill-posed problem is avoided. Furthermore, a determinate shape of the continuous MWD does not have to be assumed in order to obtain the polydispersity index. The technique has been developed to deal with entangled linear polymers, whatever the form of the MWD is. The rheological information required to obtain the polydispersity index is the storage G′(ω) and loss G″(ω) moduli, extending from the terminal zone to the plateau region. The method provides a good agreement between the proposed theoretical approach and the experimental polydispersity indices of several linear polymers for a wide range of average molecular weights and polydispersity indices. It is also applicable to binary blends.

Assessing the pH and DP of canvasses with NIR spectroscopy

The canvas support in easel paintings is composed mainly of cellulose. One of the maindegradation paths of cellulose is acid-catalysed hydrolysis, which means that in an acidic environment (low pH), its degradation proceeds at a faster rate (Strlič et al., 2005).The main effect of acid-catalysed hydrolysis is the breaking up of the polymer chains,measured by the “Degree of Polymerisation” (DP). The lowering of the DP value impliesa lower mechanical strength of the textile (Scicolone, 1993), and thus this parameter canbe used to monitor degradation. Knowing these two parameters can, therefore, be veryinformative regarding the condition of the canvas support.

Raman spectroscopy as a powerful analytical tool: probing the structure of matter

Podeu consultar el llibre complet a: http://hdl.handle.net/2445/32166

Applications of Fourier transform infrared spectroscopy

This article summarizes the basic principles of Fourier Transform Infrared Spectroscopy, with examples of methodologies and applications to different field sciences.

Photoelectron spectroscopy for surface analysis: X-ray and UV excitation

This article summarizes the basic principles of photoelectron spectroscopy for surface analysis, with examples of applications in material science that illustrate the capabilities of the related techniques.

Electron energy loss spectroscopy: physical principles, state of the art and applications to the nanosciences

In the present work we review the way in which the electron-matter interaction allows us to perform electron energy loss spectroscopy (EELS), as well as the latest developments in the technique and some of the most relevant results of EELS as a characterization tool in nanoscience and nanotechnology.

A consistent extension of the local spin density approximation to account for quantum dot mass and dielectric mismatches

A consistent extension of local spin density approximation (LSDA) to account for mass and dielectric mismatches in nanocrystals is presented. The extension accounting for variable effective mass is exact. Illustrative comparisons with available configuration interaction calculations show that the approach is also very reliable when it comes to account for dielectric mismatches. The modified LSDA is as fast and computationally low demanding as LSDA. Therefore, it is a tool suitable to study large particle systems in inhomogeneous media without much effort.

Endorectal Magnetic Resonance Imaging and Spectroscopy Are Useful for Selecting Candidates for Biopsy among Patients with Persistently Elevated Prostate Specific Antigen

To evaluate the efficacy of endorectal Magnetic Resonance Imaging (MRI) and Magnetic Resonance Spetroscopic Imaging (MRSI) combined with total prostate-specific antigen (tPSA) and free prostate-specific antigen (fPSA) in selecting candidates for biopsy. Subjects and Methods: 246 patients with elevated tPSA (median: 7.81 ng/ml) underwent endorectal MRI and MRSI before Transrectal Ultrasound (TRUS) biopsy (10 peripheral + 2 central cores); patients with positive biopsies were treated with radical intention; those with negative biopsies were followed up and underwent MRSI before each additional biopsy if tPSA rose persistently. Mean follow-up: 27.6 months. We compared MRI, MRSI, tPSA, and fPSA with histopathology by sextant and determined the association between the Gleason score and MRI and MRSI. We determined the most accurate combination to detect prostate cancer (PCa) using receiver operating curves; we estimated the odds ratios (OR) and calculated sensitivity, specificity, and positive and negative predictive values. Results: No difference in tPSA was found between patients with and without PCa (p = 0.551). In the peripheral zone, the risk of PCa increased with MRSI grade; patients with high-grade MRSI had the greatest risk of PCa over time (OR = 328.6); the model including MRI, MRSI, tPSA, and fPSA was more accurate (Area under Curve: AUC = 95.7%) than MRI alone (AUC = 85.1%) or fPSA alone (AUC = 78.1%), but not than MRSI alone (94.5%). In the transitional zone, the model was less accurate (AUC = 84.4%). The association (p = 0.005) between MRSI and Gleason score was significant in both zones. Conclusions: MRSI is useful in patients with elevated tPSA. High-grade MRSI lesions call for repeated biopsies. Men with negative MRSI may forgo further biopsies because a significantly high Gleason lesion is very unlikely

Microwave spectrometry for the Evaluation of the structural integrity of metallic stents

Purpose: To assess the feasibility of a method based on microwave spectrometry to detect structural distortions of metallic stents in open air conditions and envisage the prospects of this approach toward possible medical applicability for the evaluation of implanted stents. Methods: Microwave absorbance spectra between 2.0 and 18.0 GHz were acquired in open air for the characterization of a set of commercial stents using a specifically design setup. Rotating each sample over 360º, 2D absorbance diagrams were generated as a function of frequency and rotation angle. To check our approach for detecting changes in stent length (fracture) and diameter (recoil), two specific tests were performed in open air. Finally, with a few adjustments, this same system provides 2D absorbance diagrams of stents immersed in a water-based phantom, this time over a bandwidth ranging from 0.2 to 1.8 GHz. Results: The authors show that metallic stents exhibit characteristic resonant frequencies in their microwave absorbance spectra in open air which depend on their length and, as a result, may reflect the occurrence of structural distortions. These resonances can be understood considering that such devices behave like dipole antennas in terms of microwave scattering. From fracture tests, the authors infer that microwave spectrometry provides signs of presence of Type I to Type IV stent fractures and allows in particular a quantitative evaluation of Type III and Type IV fractures. Recoil tests show that microwave spectrometry seems able to provide some quantitative assessment of diametrical shrinkage, but only if it involves longitudinal shortening. Finally, the authors observe that the resonant frequencies of stents placed inside the phantom shift down with respect to the corresponding open air frequencies, as it should be expected considering the increase of dielectric permittivity from air to water. Conclusions: The evaluation of stent resonant frequencies provided by microwave spectrometry allows detection and some quantitative assessment of stent fracture and recoil in open air conditions. Resonances of stents immersed in water can be also detected and their characteristic frequencies are in good agreement with theoretical estimates. Although these are promising results, further verifica tion in a more relevant phantom is required in order to foresee the real potential of this approach.

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.

Reliability of the density functional approximation to describe the charge transfer and electrostatic complexes involved in the modeling of organic conducting polymers

Both the intermolecular interaction energies and the geometries for M ̄ thiophene, M ̄ pyrrole, M n+ ̄ thiophene, and M n+ ̄ pyrrole ͑with M = Li, Na, K, Ca, and Mg; and M n+ = Li+ , Na+ , K+ , Ca2+, and Mg2+͒ have been estimated using four commonly used density functional theory ͑DFT͒ methods: B3LYP, B3PW91, PBE, and MPW1PW91. Results have been compared to those provided by HF, MP2, and MP4 conventional ab initio methods. The PBE and MPW1PW91 are the only DFT methods able to provide a reasonable description of the M ̄ complexes. Regarding M n+ ̄ ␲ complexes, the four DFT methods have been proven to be adequate in the prediction of these electrostatically stabilized systems, even though they tend to overestimate the interaction energies.

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.