Spin polarized photoemission from molecular beam epitaxy-grown be-doped GaAs

We have made a comparative study of the performance of spin polarized photocathodes based on molecular beam epitaxy (MBE) grown GaAs with Be-doping and on liquid phase epitaxy (LPE) grown GaAs with Zn-doping. The experiments were performed on GaAs (100), (110), and (111) surfaces atT-300 K. The photoelectron spin polarization (P) of the MBE-photocathodes is face dependent reaching 49% for the (111) surface, a value close to P=50% predicted by theory. In contrast for the LPE-photocathodes P is significantly lower (19P36%). Possible causes for the higher polarization of the MBE-photocathodes are investigated. The influence of the Zn- and Be-dopant is elucidated by theoretical model calculations which shows that replacing the Zn-dopant by Be reduces significantly the depolarization at very low temperatures, but not at room temperature. It is therefore concluded that theinterface region between the GaAs substrate and the MBE-GaAs layer grown on top of it strongly influences the performance of the source.On leave from the Istituto di Fisica Universitá di Modena I-41100 Modena Italy.     

Experimental Determination of the Electronic Polarizability of Quinoline and Isoquinoline in Solution by Three New Strategies

The values of electronic polarizability of quinoline and isoquinoline in extremely diluted liquid solution are reported in this paper. These were obtained by means of three new strategies based on UV-visible-NIR spectroscopy, the Kramers-Krönig relations, high precision densitometry and high exactitude refractometry, which are called here Arakawa’s Approximation (AA), Optical Substractive Approximation (OSA) and Optical Differential Approximation (ODA). In general the static electronic polarizability values of solute molecules obtained by ODA and OSA are in excellent agreement with the reported theoretical values at the Density Functional Theory (DFT) level and the Atom monopole-dipole model, but strong discrepancies were observed with the experimental values previously reported for quinoline and isoquinoline using refractometric and electro-optic methods. These differences were interpreted and analyzed in terms of dielectric intermolecular forces, resonant and pre-resonant effects. The AA method is shown to fail in predicting the polarizability of the quinoline and isoquinoline molecules.     

A Direct Synthesis of Aromatic Nitriles from Aldehydes Using a Mexican Bentonite and Microwave or Infrared Irradiation,in Absence of Solvent

An efficient and simple procedure for the direct conversion of aromatic Aldehydes into the corresponding nitriles with hydroxylamine hydrochloride and a Mexican Bentonite via infrared or microwave irradiation.     

SIMS studies of polymeric tertiary structures in monolayers: Polysiloxane helical coil structures

A static SIMS study was performed using poly(dimethyl siloxane) (PDMS) as a model system to investigate the effects of tertiary structure on the ion formation mechanism and ion formation probability of fragments in the high mass region (>1000 Da). PDMS produced from anionic polymerization with a narrow polydispersity, can form well-ordered helically coiled monolayers using Langmuir-Blodgett methods at the air water interface, either in a hairpin configuration, if the endgroups are functional or as flat helically coiled chains. Reflection absorption Fourier transform infrared (RA-FTIR) spectroscopic analysis shows the changes in bonding between flat helically coiled PDMS and cast films from dilute solvents, which produces a random coil configuration. Differences between the model systems in infrared spectrum show evidence of changes in structure, producing variation in band formation. Also observed are changes in the band shape and relative peak area between the model systems. These polymeric changes translate into differences in the relative intensities of fragments formed in the repeating pattern of clusters in the high mass ToF-SIMS spectra of the ordered versus the random cast films. Both statistical chain break analysis and molecular mechanics simulations of structure are used to support the analysis.     

Hydrogen storage inside a toroidal carbon nanostructure C120: Density functional theory computer simulation

Ab initio density functional calculations were performed for a toroidal carbon C₁₂₀ nanostructure. Hydrogen molecules, n = 1–15, were added inside the nanotorus and for each one of these systems a geometry optimization was obtained. The cohesive energy shows that these structures are energetically stable. For example, the binding energies are ?34.95 and ?36.19 Hartrees and the interatomic distances H? H are 0.753 and 0.772 Å for 1 and 14 molecules, respectively. Considering only molecular hydrogen, we have always seen so far weak physisorption into the C₁₂₀ nanotorus. There is no chemisorption until the number oh hydrogen molecules are increased to 14. In this case, four hydrogen atoms are chemisorbed. With 15 molecules, there are 10 hydrogen atoms chemisorbed just at the inner nanotorus surface forming 10 H? C bondings with bond length close to that in methane. © 2010 Wiley Periodicals, Inc. Int J Quantum Chem 110:2495–2508, 2010     

2D H and C NMR conformational studies of thienopyridines and carboline biarylic compounds

In this paper, we report on conformational studies of biarylic compounds, as prepared through the well-known aza-Wittig methodology. The conformational studies were mainly realized by bidimensional (2D) nuclear magnetic resonance spectroscopy (NMR) and NOESY experiments. The conformational behavior showed that these biarylic compounds display an orthogonal symmetry and adopt a characteristic arrangement around the pivotal bond. Molecular modeling calculations were performed to support structure conformations.     

Asymmetric Diels-Alder reactions of chiral cyclopropylidene imide dienophiles: preparation of gem-dimethyl- and spirocyclopropane norbornyl carboxylic acids

A highly efficient strategy has been developed for the rapid asymmetric synthesis of gem-dimethyl and spirocyclopropyl norbornyl carboxylic acids. The key transformation involved the unprecedented asymmetric Diels-Alder reaction of highly reactive beta,beta-cyclopropyl-alpha,beta-unstaturated N-acyloxazolidinones with cyclopentadiene affording the adducts in high yield and de.     

Experimental and Theoretical Determination of the Limiting Partial Molar Volume of Indole in CCl<Subscript>4</Subscript>, Tetrahydrofuran and Acetonitrile at 293.15 K: A Comparative Study with Benzimidazole and Benzothiophene

The partial molar volumes of indole(Ind) at infinite dilution (V₂^￥V_{2}^{\infty}) in carbon tetrachloride (CCl₄), acetonitrile (ACN) and tetrahydrofuran (THF) as solvents, were estimated from densitometry measurements at 293.15 K. The results indicate that $V_{2}^{\infty}\mbox{(ACN)}>V_{2}^{\infty}\mbox{(CCl$V_{2}^{\infty}\mbox{(ACN)}>V_{2}^{\infty}\mbox{(CCl $\approx V_{2}^{\infty}\mbox{(THF)}$\approx V_{2}^{\infty}\mbox{(THF)}. The values determined in this study are close to the values calculated from reported density for Ind in the solid state. In order to make a comparison the partial molecular volume of benzimidazole (Bim) and benzothiophene (BT) in solvents with appropriate solubility were measured too, and the results have revealed that $V_{2}^{\infty}\mbox{(BT)}>V_{2}^{\infty}\mbox{(Ind)}$V_{2}^{\infty}\mbox{(BT)}>V_{2}^{\infty}\mbox{(Ind)} in CCl₄ and $V_{2}^{\infty}\mbox{(Ind)}>V_{2}^{\infty}\mbox{(Bim)}$V_{2}^{\infty}\mbox{(Ind)}>V_{2}^{\infty}\mbox{(Bim)} in THF. In this work the role of solvent reorganization around to solute cavity, and specific and nonspecific interactions on the volumetric behavior of these molecules in solution are discussed using the Terasawa-Itsuki-Arakawa model, the Lee-Graziano model, molar volumes of solutes calculated at the DFT-B3LYP/cc-pVTZ and aug-cc-pVTZ level in the gas phase and considering solvent presence with the Onsager’s reaction field, and the van der Waals volume. This analysis suggests that the molecular volumes of solutes are overestimated by the quantum methods employed in this work and that the volumetric contribution from the van der Waals components to the limiting partial molecular volumes of solutes is important, with the exception of Ind in CCl₄ where the solvent reorganization is the dominant factor.