Perspectives on double-excitations in TDDFT

The adiabatic approximation in time-dependent density functional theory (TDDFT) yields reliable excitation spectra with great efficiency in many cases, but fundamentally fails for states of double-excitation character. We discuss how double-excitations are at the root of some of the most challenging problems for TDDFT today. We then present new results for (i) the calculation of autoionizing resonances in the helium atom, (ii) understanding the nature of the double excitations appearing in the quadratic response function, and (iii) retrieving double-excitations through a real-time semiclassical approach to correlation in a model quantum dot.     

Facile and stereo-controlled synthesis of 2-deoxynojirimycin, Miglustat and Miglitol

A novel and facile synthesis of a series of the biologically significant iminosugar derivatives including 2-deoxynojirimycin, Miglustat and Miglitol is reported. The synthesis features a strategic double inversion mechanism for securing the desired stereochemistry at C5 position of such glucose-type carbohydrate mimetics, representing a practical and remarkable improvement on the previously reported method that suffers from the loss of the stereo-control during the reaction process.     

FeCl3 catalysed two consecutive aminomethylation at the α-position of the β-dicarbonyl compounds: an easy access to hexahydropyrimidines and its spiro analogues

Multicomponent synthesis of 1,3-diaryl-hexahydropyrimidines by a one-pot reaction of 1,3-dicarbonyl compounds, amines and formaldehyde catalysed by FeCl₃ in dichloromethane at room temperature (25-30 °C) has been reported. Double amino methylation occurs at the α-position of the 1,3-dicabonyl compounds/β-keto esters. The same methodology leads to spiro compounds with indane-1,3-dione. In this reaction, six molecules condense in one pot to form six new covalent bonds, thus, creating high atom economy. This is the first report of the synthesis of the substituted hexahydropyrimidines involving β-keto esters and its spiro analogues with indane-1,3-dione.     

双梳型共聚物在莠去津颗粒表面吸附的X射线光电子能谱分析

采用X射线光电子能谱(XPS)研究了双梳型共聚物吸附于莠去津颗粒样品表面的电子状态,计算了吸附厚度.结果表明:吸附后,莠去津颗粒界面的N 1s和Cl 2p谱峰强度明显减弱,Cl 2s几乎消失,而C 1s和O1s谱峰强度则明显增强,这主要是双梳型共聚物中C和O的贡献,且吸附后能在莠去津颗粒界面形成良好的吸附保护膜,其厚度...     

Formation of double helix self-assembled monolayers of ethynylhelicene oligomer disulfides on gold surfaces

Optically active ethynylhelicene pentamers and hexamers linked by disulfide bonds were synthesized. They formed self-assembled monolayers (SAMs) with double helix structure on gold surfaces, which were analyzed by infrared reflection-absorption spectroscopy (IR-RAS), quartz crystal microbalance (QCM), surface plasmon resonance (SPR), and circular dichroism (CD). Double helix SAMs could be formed on gold surfaces either from double helices or random coils in solution. The double helices on the surface were more stable than in solution. This result suggested the presence of strong intercomplex interactions between double helix complexes on the surface.     

Comparison of two laser-induced breakdown spectroscopy techniques for total carbon measurement in soils

The potentials of two advanced laser-induced breakdown spectroscopy (LIBS) techniques which are used to determine the total carbon content in soils have been examined. The first one is the combination of a single-pulse laser ablation with spark excitation of plasma plume triggering the gap between electrodes close to the target surface. The second one is a more conventional double-pulse LIBS. In both modes the calibration graphs have a nonlinear trend in the actual range of carbon contents and present a good R² value (0.97). In the combined laser-spark approach, using low-cost and portable laser instrumentation is possible, as well as inducing a micro-damage on the target surface. Certain regularities in the spectral line intensities of soil nutritious elements have been detected and appear to be connected to the total carbon content and to the soil origin.     

A stereoselective total synthesis of (−)-seychellene

A stereoselective total synthesis of the tricyclic sesquiterpene (−)-seychellene, starting from (R)-carvone via (R)-3-methylcarvone has been accomplished, employing a combination of intermolecular Michael addition-intramolecular Michael addition sequence, a stereoselective hydrogenation, and an intramolecular alkylation reaction.     

Double bond isomerization of 5-vinylbicyclo[2.2.1]hept-2-ene to 5-ethylidenebicyclo[2.2.1]hept-2-ene over alkaline earth oxides

All the alkaline earth oxides exhibit activities for double, bond isomerization of 5-vinylbicyclo[2.2.1]hept-2-ene (VBH) to 5-ethylidenebicyclo[2.2.1]hept-2-ene (EBH) at a reaction temperature of 273 K. The order of the activity on the basis of unit weight of catalyst was CaO>MgO>SrO>BaO when compared under optimum pretreatment conditions. The E/Z ratio in the products is determined by the reaction temperature regardless of the type of catalyst; the ratios were 82/18 and 88/12 for the reaction temperatures of 323 and 273 K, respectively.     

Non-Newtonian effects of second-order fluids on double-layered porous Rayleigh-step bearings

Theoretical study of double-layered porous Rayleigh-step bearings with second-order fluid as lubricant is presented. An approximate method for the solutions of the governing fluid film equations for a porous region is proposed. The expressions for the pressure distribution, load capacity and frictional coefficient are obtained in compact form. Calculations of the dimensionless load capacity, frictional force and frictional coefficients are presented for specific values of the material parameters. It is found that the double porous layer yields an increase in the load capacity and ensures decrease in frictional force at the porous lining as compared with the conventional porous Rayleigh-step bearings. The maximum dimensionless load-carrying capacity is found to occur at a slightly larger step ratio as compared with the conventional porous Rayleigh-step bearings.     

Consolidation around a borehole embedded in media with double porosity under release of geostatic stresses

The paper deals with the stress, displacement, pore and fissure pressures fields induced by the drilling and/or the pressurization of a vertical borehole in a formation of water-saturated porous media with double porosity. The solution includes the boundary condition of non-hydrostatic in situ state of stress. The solid skeleton is assumed to behave as a linearly poroelastic material with compressible constituents. The analytical solution is derived in Laplace’s space and transformed to the time domain using a numerical inversion technique. The histories of pore and fissure pressures are illustrated to show the influence of permeabilities of the pore and fissure systems.