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91.
A general numerical method and program for simulation of the kinetics of multistep reactions is described, with details for collation of data, construction of a mechanistic model, and simulation of reciprocal relaxation times and calculation of individual rate constants. The working scheme of the program includes an initial approximate simulation by adjustment of the rate constants followed by their optimization with a Powell minimization subroutine. The procedure is applied to aromatic nucleophilic addition. 相似文献
92.
93.
Abstract
Classic examples of low-Reynolds recirculating cavity flows are typically generated from lid-driven boundary motion at a solid–fluid interface, or alternatively may result from shear flow over cavity openings. Here, we are interested in an original family of boundary-driven cavity flows occurring, in contrast to classic setups, at fluid–fluid interfaces. Particle image velocimetry (PIV) is used to investigate the structure of internal convective flows observed in thin liquid shells. Under the specific configuration investigated, the soap bubble’s liquid shell is in fact in motion and exhibits sporadic local “bursts”. These bursts induce transient flow motion within the cavity of order Re ∼ O(1). The combination of PIV and proper orthogonal decomposition (POD) is used to extract dominant flow structures present within bubble cavities. Next, we show that thermally induced Marangoni flows in the liquid shell can lead to forced, (quasi) steady-state, internal recirculating flows. The present findings illustrate a novel example of low-Reynolds boundary-driven cavity flows. 相似文献94.
We studied the photon spectrum in coated microspheres with alternating quasiperiodic layers having left-handed (LH) materials included. It is found that the band gap (spectral zone of nearly zero transmittancy) in such a system is strongly enhanced. At an increase of the quasiperiodicity parameter γ, the boundaries of the spectral band gaps acquire the intended shape. When γ exceeds the inverse golden mean value, a structure with extremely narrow separated resonant peaks with nearly complete transmittance arises. At increased γ, such resonances migrate to the center of the band gap. This effect allows creating optical filters with extremely narrow passbands. 相似文献
95.
If we disregard the shape of the boundary hysteresis loop, H1 for SBA-15, MCM-41 and KIT-6, H2 for p+-type porous silicon and porous glass, the hysteretic features inside the loop are qualitatively the same for all these systems and show that none of them are composed of independent pores whether the pores are interconnected or not. We hence believe that the physical parameter which couples the pores is not the interconnectivity but the elastic deformation of the porous matrix. The thermodynamic approach we develop includes the elastic energy of the solid. We show that the variation of the surface free energy, which is proportional to the deformation of the porous matrix, is an important component of the total free energy. With porous silicon, we experimentally show that a stress external to the porous matrix exerted by the substrate on which it is supported significantly increases the total free energy and the adsorbed amount and decreases the condensation pressure compared to that of the same porous matrix detached from its substrate which is the relaxed state of the supported layer. This stress can be partly relaxed by making thicker porous layers due to the breaking of Si-Si bonds. This results in the shift of the isotherms towards that of the membrane. We propose a new interaction mechanism occurring through the pore wall elastic deformation in which the external mechanical stress is imposed on a given pore by its neighbours. 相似文献
96.
Maté B Ortega IK Moreno MA Herrero VJ Escribano R 《The journal of physical chemistry. B》2006,110(14):7396-7401
An investigation of orientation effects in films of nitric acid dihydrate (NAD) is presented, based on a systematic study of transmission and reflection-absorption infrared (RAIR) spectra of samples of varying thickness. The samples are prepared by vapor deposition on Ge (for transmission spectroscopy) and on Al substrates (for RAIR spectroscopy) at 175 K to produce crystalline alpha-NAD films. Transmission spectra were recorded at normal incidence, and RAIR spectra were recorded at a grazing angle of 75 degrees, with polarized radiation. The observed spectra are compared with predictions of a classical Fresnel model, to test the available optical indices of NAD, which are of great importance for the accurate interpretation of data from remote sensing measurements. Whereas the procedure yields satisfactory results for transmission and s-polarized RAIR spectra, it is found that the agreement is not acceptable for p-polarized RAIR spectra. An explanation is suggested in terms of a preferential alignment of the films, with the (10-1) crystallographic plane of the crystal situated parallel to the substrate. The infrared activity of a band at approximately 1170 cm(-1) is explained in terms of a preferential orientation of the crystal domains in the film. 相似文献
97.
[STRUCTURE: SEE TEXT] Cis-2,8-disubstituted oxocanes and the parent unsaturated precursors were prepared from the corresponding Co2(CO)6-cycloalkynic ethers. Key steps in such synthesis were the ether linkage formation by intermolecular Nicholas reaction, RCM of the suitable acyclic dienyl ether and montmorillonite K-10 induced isomerization of the complexed cycloalkyne. A short synthesis of (+)-cis-lauthisan taking advantage of the developed methodology is described. 相似文献
98.
D. V. Roshchupkin O. A. Plotitsyna R. R. Fakhrtdinov D. V. Irzhak A. I. Erko L. Ortega 《Journal of Surface Investigation: X-ray, Synchrotron and Neutron Techniques》2013,7(4):659-662
The process of the excitation and propagation of pseudosurface acoustic waves in crystals of the langasite family is studied via X-ray diffractometry for the first time. The investigations are carried out using the BESSY II synchrotron radiation source in the double-crystal X-ray diffractometer scheme. The process of pseudosurface acoustic wave propagation is studied based on an analysis of the diffraction spectra of acoustically modulated crystals. Both the velocities of the pseudosurface acoustic waves and the power flow angles of the acoustic energy are measured for the first time. The pseudosurface acoustic wave is shown to be flowing. Surface and pseudosurface acoustic waves generated by an interdigital transducer in the Z cut of a La3Ga5.5Ta0.5O14 crystal are compared. 相似文献
99.
Control charts are the most popular tool for monitoring production quality. In traditional control charts, it is usually supposed that the observations follow a multivariate normal distribution. Nevertheless, there are many practical applications where the normality assumption is not fulfilled. Furthermore, the performance of these charts in the presence of measurement errors (outliers) in the historical data has been improved using robust control charts when the observations follow a normal distribution. In this paper, we develop a new control chart for t‐Student data based on the trimmed T2 control chart () through the adaptation of the elements of this chart to the case of this distribution. Simulation studies show that a control chart performs better than T2 in t‐Student samples for individual observations. Copyright © 2012 John Wiley & Sons, Ltd. 相似文献
100.
Alice E. Dearle Daniel J. Cutler Hector W. L. Fraser Sergio Sanz Edward Lee Sourav Dey Ismael F. Diaz‐Ortega Gary S. Nichol Hiroyuki Nojiri Marco Evangelisti Gopalan Rajaraman Jürgen Schnack Leroy Cronin Euan K. Brechin 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(47):17059-17062
The dissolution of anhydrous iron bromide in a mixture of pyridine and acetonitrile, in the presence of an organic amine, results in the formation of an [Fe34] metal oxide molecule, structurally characterised by alternate layers of tetrahedral and octahedral FeIII ions connected by oxide and hydroxide ions. The outer shell of the complex is capped by a combination of pyridine molecules and bromide ions. Magnetic data, measured at temperatures as low as 0.4 K and fields up to 35 T, reveal competing antiferromagnetic exchange interactions; DFT calculations showing that the magnitudes of the coupling constants are highly dependent on both the Fe‐O‐Fe angles and Fe?O distances. The simplicity of the synthetic methodology, and the structural similarity between [Fe34], bulk iron oxides, previous FeIII–oxo cages, and polyoxometalates (POMs), hints that much larger molecular FeIII oxides can be made. 相似文献