Development of the Hamiltonian and transition moment operators of symmetric top molecules using the O (3) ⊃ C∞v ⊃ C3v group chain

We present a development of the Hamiltonian, dipole moment, and polarizability operators for XY₃Z molecules. These rovibrational operators are written with the aid of a tensorial formalism derived from the one already used in Dijon and adapted to the XY₃Z symmetric tops in a recent paper [A. El Hilali, V. Boudon, M. Loëte, J. Mol. Spectrosc. 234 (2005) 166-174]. We use the O (3) ⊃ C_∞v ⊃ C_3v group chain. Expressions for the matrix elements are derived for these operators.     

Approaches for quantitative Auger electron spectroscopy of silicon after high dose nickel implantation

Summary Silicon samples of well-known nickel content have been produced by ion implantation in the dose range from 10¹⁷ to 10¹⁸ Ni/cm². Such implants are used for the comparison of different approaches for quantitative Auger electron analysis. Considerable differences are found between results obtained from peak-to-peak heights in the differentiated energy spectrum, neglecting composition-dependent changes of the line widths, and those results calculated with consideration of variations of the line widths. Matrix effects are taken into account by the inclusion of backscattering factors and escape depths. The results show that the elemental composition for the Ni/Si system cannot be accurately determined over the whole dose range. The discrepancies are attributed to sputter-induced composition changes or incorrect theoretical matrix factors.     

Simultaneous analysis of 13C‐glutathione as its dimeric form GSSG and its precursor [1‐13C]glycine using liquid chromatography/isotope ratio mass spectrometry

Determination of glutathione kinetics using stable isotopes requires accurate measurement of the tracers and tracees. Previously, the precursor and synthesized product were measured with two separate techniques, liquid chromatography/isotope ratio mass spectrometry (LC/IRMS) and gas chromatography/combustion/isotope ratio mass spectrometry (GC/C/IRMS). In order to reduce sample volume and minimize analytical effort we developed a method to simultaneously determine ¹³C‐glutathione as its dimeric form (GSSG) and its precursor [1‐¹³C]glycine in a small volume of erythrocytes in one single analysis. After having transformed ¹³C‐glutathione into its dimeric form GSSG, we determined both the intra‐erythrocytic concentrations and the ¹³C‐isotopic enrichment of GSSG and glycine in 150 µL of whole blood using liquid chromatography coupled to LC/IRMS. The results show that the concentration (range of µmol/mL) was reliably measured using cycloleucine as internal standard, i.e. with a precision better than 0.1 µmol/mL. The ¹³C‐isotopic enrichment of GSSG and glycine measured in the same run gave reliable values with excellent precision (standard deviation (sd) <0.3‰) and accuracy (measured between 0 and 5 APE). This novel method opens up a variety of kinetic studies with relatively low dose administration of tracers, reducing the total cost of the study design. In addition, only a minimal sample volume is required, enabling studies even in very small subjects, such as preterm infants. Copyright © 2009 John Wiley & Sons, Ltd.     

The defocussed X-ray interferometer

The influence of a different distance between beam splitterS and mirror crystalM on one hand and analyser crystalA on the other (“defocus” Δx) on the structure and the contrast of the fringe pattern of a Laue-case interferometer is investigated both experimentally and theoretically. A nonzero Δx generates a typical additional pattern which is superimposed on any ordinary interference pattern to be studied with the instrument. Δx≠0 also impairs the fringe contrast. In order not to loose all contrast ¦Δx¦ must be kept below 25 to 100 microns, the exact value depending on the wave length and the reflection used. The influence of other misalignments on the pattern is also assessed. The agreement between theory and the experiments is very good.     

Rational Design of Poly(2,7‐Carbazole) Derivatives for Photovoltaic Applications

A reliable model that can be used to estimate the electronic properties (i.e., the HOMO, LUMO, and band gap energies) of conjugated polymers would be a great tool for applications in organic electronics such as light‐emitting diodes, field‐effect transistors, and photovoltaic cells. Recently, poly(2,7‐carbazole) derivatives have shown promising results when used as an active donor layer in bulk heterojunction photovoltaic cells with power conversion efficiency exceeding 7%. By using a simple correlation between density functional theory (DFT) theoretical calculations performed on six model compounds (using the repeating unit) and experimental data from the six corresponding polymers, an accurate estimation of the HOMO energy level, the LUMO energy levels, and the band gap of several poly(2,7‐carbazole) derivatives was obtained. According to the theoretical data obtained for more than one hundred repeating units, fourteen new copolymers that can be used as p‐type materials in bulk heterojunction solar cells were selected and synthesized. Experimental data obtained from these materials were then used to refine the correlation between DFT and experimental data of poly(2,7‐carbazole) derivatives.

     

Nonlinear susceptibility measurements in a supercooled liquid close to Tg: Growth of the correlation length and possible critical behavior

The existence of a growing correlation length associated with the strong increase of relaxation times of glass-formers close to the glass transition is still a major open question in glass physics. It has been recently proposed that the ac nonlinear susceptibility of a supercooled liquid close to the glass transition temperature T_g would be a probe of dynamical correlations. As for spin glasses, where the nonlinear susceptibility diverges at the transition, this quantity is tailored to reveal the possible “hidden” critical behavior of the glass transition. We have developed a high sensitivity experimental device to measure the nonlinear dielectric susceptibility of an insulating material at finite frequency. It measures the third harmonics of the current flowing out of a capacitor with the supercooled liquid as the dielectric layer. It is based on a bridge with two capacitors, and reaches a sensitivity better than 10^− 7 (ratio of third to first harmonics). Our first results on supercooled glycerol are presented. They clearly reveal the growing of the correlations close to the glass transition.     

Improved method for the iodine(III)-mediated preparation of aryl sulfonimidates

[reaction: see text] One-pot hypervalent iodine-mediated oxidations of arylsulfinamides to arylsulfonimidates is reported. Contrary to the case of alkylsulfinamides, use of iodosobenzene was not satisfactory. The reaction worked best with diacetoxyiodosobenzene (DIB) and a mild base (MgO). The influence of substituents on the iodine(III) reagent arene has been examined.     

TD-DFT investigation of the UV spectra of pyranone derivatives

The UV absorption spectra of more than 80 substituted coumarins and chromones have been investigated with the PCM-TD-DFT theoretical scheme using three hybrid functionals (O3LYP, B3LYP, and PBE0) and taking into account methanol or ethanol solvation effects. For most of the studied derivatives, there are at least two allowed excited states presenting a strong oscillator strength in the UV region. The first allowed excitation is associated to a HOMO-LUMO transition whereas the second corresponds to a transition from the HOMO-1 to the LUMO. Both involve a charge transfer from the benzenic cycle to the pyranone moiety. Statistically treating the PBE0 results allows a prediction of the lambda(max) with small standard deviations: in methanol, 6 nm (0.07 eV) for the first excitation (lambda(max)(1)) and 5 nm (0.08 eV) for the second one (lambda(max)(2)), whereas in ethanol 6 nm (0.08 eV) for (lambda(max)(1)) and 6 nm (0.13 eV) for (lambda(max)(2)).