Rhodium-catalyzed asymmetric cyclodimerization of oxabenzonorbornadienes and azabenzonorbornadienes: scope and limitations

Cationic rhodium(I)-catalyzed cyclodimerization of oxabenzonorbornadienes produced naphtho[1,2-b]furan ring systems in a single step with excellent yields and excellent enantioselectivities. The effect of various Rh(I) catalysts, Ag(I) salts, solvents, and phosphine ligands on the yield and enantioselectivity of the reaction was investigated, and the scope and limitations of this reaction with various oxabicyclic alkenes were studied. Similar results were obtained with the azabenzonorbornadiene analogues, providing the corresponding cyclodimerization products in excellent yields and excellent enantioselectivities.     

Steric and electronic effects relating to the Cu2+ Jahn-Teller distortion in Zn(1-)xCuxAl2O4 spinels

Zn1-xCuxAl2O4 (0相似文献   

In-plane stacking disorder in polydisperse hard sphere crystals

We demonstrate that in random-stacking hard-sphere colloidal crystals the stacking disorder not only exists in the direction perpendicular to the close-packed layers, but also extends in the lateral direction. The existence of such in-plane stacking disorder is suggested by a recent observation of lateral broadening of the Bragg scattering rods in microradian X-ray diffraction and is further confirmed here by real-space confocal microscopy in two hard-sphere colloidal systems with different relative gravity effects. Due to the in-plane stacking disorder, the hexagonal planes consist of islands with different lateral A, B, and C positions with characteristic line defects in between them. The real-space layer-by-layer stacks of images also reveal the 3-D structure of the defects. The chance zeta to find another line-defect above a line-defect in the layer below turns out to be close to 1/2--independent of relative gravity--which can be explained by the two different stacking options above a defect. The stacking of a few sets of several line defects situated on top of each other turns out to be predominantly FCC-like.     

Technology choice under several uncertainty sources

We analyze a model of irreversible investment with two sources of uncertainty. A risk-neutral decision maker has the choice between two mutually exclusive projects under input price and output price uncertainty. We propose a complete study of the shape of the rational investment region and we prove that it is never optimal to invest when the alternative investments generate the same payoff independently of its size. A key feature of this bidimensional degree of uncertainty is thus that the payoff generated by each project is not a sufficient statistic to make a rational investment. In this context, our analysis provides a new motive for waiting to invest: the benefits associated with the dominance of one project over the other. As an illustration, we apply our methodology to power generation under uncertainty.     

Direct test of laser tunneling with electron momentum imaging

Tunneling is often used to describe multiphoton ionization of rare gas atoms in infrared fields. We test the tunneling approximation and its nonadiabatic extension by measuring the unperturbed momentum distribution along the κ direction of a circularly polarized light pulse. We find substantial, but not total, agreement between our results and the predictions of the model. As predicted, the κ direction momentum distribution is Gaussian and its width increases with the square root of electric field strength. However, the width is 15% too large and we find no evidence of nonadiabatic effects as we approach the expected limits of the approximation.     

Attosecond temporal gating with elliptically polarized light

Temporal gating allows high accuracy time-resolved measurements of a broad range of ultrafast processes. By manipulating the interaction between an atom and an intense laser field, we extend gating into the nonlinear medium in which attosecond optical and electron pulses are generated. Our gate is an amplitude gate induced by ellipticity of the fundamental pulse. The gate modulates the spectrum of the high harmonic emission and we use the measured modulation to characterize the sub-laser-cycle dynamics of the recollision electron wave packet.     

Water exclusion at the nanometer scale provides long-term passivation of silicon (111) grafted with alkyl monolayers

This work is a quantitative study of the conditions required for a long-term passivation of the interface silicon-alkyl monolayers prepared by thermal hydrosilyation of neat 1-alkenes on well-defined H-Si(111) surfaces. We present electrochemical capacitance measurements (C-U) in combination with ex situ atomic force microscopy (AFM) observations and X-ray photoelectron spectroscopy (XPS) measurements. Capacitance measurements as a function of the reaction time and XPS data reveal close correlations between the chemical composition at the interface and its electronic properties. A very low density of states is found if suboxide formation is carefully prevented. The monitoring of C-U plots and AFM imaging upon exposure of the sample in diverse conditions indicate that the initial electronic properties and structure of the interface are long-lasting only when the monolayer surface coverage is theta > 0.42. A model demonstrates that this threshold value corresponds to a monolayer with intermolecular channels narrower than approximately 2.82 A, which is equal to the diameter of a water molecule. Water exclusion from the monolayer promotes long-term passivation of the silicon surface against oxidation in air and water as well as perfect corrosion inhibition in 20% NH(4)F. We provide two criteria to assess when a sample is optimized: The first one is an effective dielectric constant <2.5, and the second one is a very characteristic energy diagram at open circuit potential.     

Ultrasmooth silver thin film electrodes with high polar liquid wettability for OLED microcavity application

For a lab-on-chip application, we fabricate a blue bottom emitting strong microcavity organic light emitting diode (OLED), using very smooth and optically thin (25 nm) silver film as anode on a glass substrate. To improve the hole injection in the OLED device, PEDOT-PSS (poly(3,4-ethylenedioxythiophene)-poly(styrene sulfonic acid)) has been used, so the silver anode must present not only a very smooth surface but also a strong adherence on the glass and a high wettability to allow a good PEDOT-PSS spin coating deposition. To obtain these physical properties, different 5 nm thick nucleation layers (germanium, chromium, and hydrogenated amorphous carbon) have been used to grow the silver thin films by e-beam deposition. The Ge/Ag bilayer presents all the desired properties: this bilayer, investigated by ellipsometry, optical profilometry, contact angle measurements, and XPS analysis, highlights an ultrasmooth surface correlated with the film growth mode and a high wettability related to its surface chemical composition.     

Probing the spatial structure of a molecular attosecond electron wave packet using shaped recollision trajectories

Using orthogonally polarized 800 nm and 400 nm laser pulses, we have generated high harmonics in ethane (C(2)H(6)). We observe that the intensity of each harmonic order modulates with the attosecond delay between the two laser fields. The modulation period of the low even harmonics is twice that of the period of modulation of the other harmonics. By comparing with theoretical calculation, we show that the double periodicity is a result of the electron wave packet motion in the valence shell of C(2)H(6) on the attosecond time-scale. Our method is a general approach to measuring internal electron dynamics which does not require molecular alignment, making it applicable to more complex molecules than previous approaches.     

Partitioning of the linear photon momentum in multiphoton ionization

The balance of the linear photon momentum in multiphoton ionization is studied experimentally. In the experiment argon and neon atoms are singly ionized by circularly polarized laser pulses with a wavelength of 800 and 1400 nm in the intensity range of 10(14)-10(15) W/cm2. The photoelectrons are measured using velocity map imaging. We find that the photoelectrons carry linear momentum corresponding to the photons absorbed above the field free ionization threshold. Our finding has implications for concurrent models of the generation of terahertz radiation in filaments.