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81.
Meier R Maigut J Kallies B Lehnert N Paulat F Heinemann FW Zahn G Feth MP Krautscheid H van Eldik R 《Chemical communications (Cambridge, England)》2007,(38):3960-3962
The equilibrium between the twist-boat (tb) and half-chair (hc) conformers of the central diamine chelate ring of [Fe(III)(tmdta)]- in solids and aqueous solution has been studied by Raman spectroscopy, supported by calculated Raman spectra using Density Functional Theory. 相似文献
82.
Dieltiens N Moonen K Stevens CV 《Chemistry (Weinheim an der Bergstrasse, Germany)》2007,13(1):203-214
A new tandem reaction sequence has been developed for the synthesis of 2-phosphono pyrroles. The sequence consists of ring-closing enyne metathesis of a substituted aminophosphonate, containing a terminal alkyne and an internal alkene, in combination with in situ oxidation of the produced 3-pyrrolines using tetrachloroquinone. By analyzing the formation of the end and certain byproducts, taking into account the difference in reactivity of different substrates and carefully studying spectroscopic data, it was found that the reaction proceeds by means of the "yne-then-ene" pathway. During the initiation phase, a new ruthenium carbene is formed which continues the propagation cycle. 相似文献
83.
Reversible diffusion limited cluster aggregation of hard spheres with rigid bonds was simulated and the self-diffusion coefficient was determined for equilibrated systems. The effect of increasing attraction strength was determined for systems at different volume fractions and different interaction ranges. It was found that the slowing down of the diffusion coefficient due to crowding is decoupled from that due to cluster formation. The diffusion coefficient could be calculated from the cluster size distribution and became zero only at infinite attraction strength when permanent gels are formed. It is concluded that so-called attractive glasses are not formed at finite interaction strength. 相似文献
84.
J.C. Gimel T. Nicolai D. Durand J.M. Teuler 《The European Physical Journal B - Condensed Matter and Complex Systems》1999,12(1):91-97
Dynamic properties of Brownian particles immersed in a periodic potential with two barriers V1 and V2 (symmetric bistable potential) are studied by using the Fokker-Planck equation which we solve numerically by the matrix continued
fraction method. This study will therefore serve to demonstrate the influence of this form of potential, which is of great
interest for superionic conductors and for many other solid systems, on the diffusion process. Thus, we have calculated the
full width at half maximum (FWHM) ) of the quasi-elastic line of the dynamic structure factor, for a large range of values of the wave-vectors q. Our results show clearly that, by varying the ratio of the barriers strictly between and 1, the Fokker-Planck equation describes a diffusive process which has some characteristic of jump and
liquid-like regimes. While in the limit cases, i.e. when tends to or 1, the diffusion process can be described only by a simple jump motion. However, the jump-lengths corresponding
to each limit case are not equal. In general the change of the ratio is found to have a significant effect on the character
of the diffusive motion. We have also performed Fokker-Planck dynamics calculations of the diffusion coefficient in a bistable
potential. We have found a good agreement between numerical calculations and analytical approximation results obtained in
the high friction limit.
Received 25 May 1998 and Received in final form 15 November 1998 相似文献
85.
Victor N. Vasilets Anatolii V. Kovalchuk Tat'yana I. Yuranova Ardalion N. Ponomarev Raisa V. Talroze Nicolai A. Plate 《先进技术聚合物》2000,11(7):330-333
The orientation behavior of a nematic side‐chain polymer grafted on polytetrafluoroethylene (PTFE) is studied. The sandwich‐like composite was prepared by the graft post‐polymerization of 4‐cyan‐4′‐(biphenyloxy)butyl acrylate on a PTFE film pretreated by vacuum ultraviolet irradiation (VUV). The oriented liquid crystal layer was prepared by mechanical stretching of the composite film. Orientation degree was measured by means of FT‐IR spectroscopy. The orientation function increases with the increasing strain and attains the upper limit value at the strain Δl/l > 1.0. The temperature dependence of the orientation degree is completely reversible under cooling and heating. Copyright © 2000 John Wiley & Sons, Ltd. 相似文献
86.
87.
In supramolecular chemistry, the rational design of self-assembled systems remains a challenge. Herein, hydrogen-bonded rosettes of melamine and ammeline have been theoretically examined by using dispersion-corrected density functional theory (DFT-D). Our bonding analyses, based on quantitative Kohn–Sham molecular orbital theory and corresponding energy decomposition analyses (EDA), show that ammeline is a much better building block than melamine for the fabrication of cyclic complexes based on hydrogen bonds. This superior capacity is explained by both stronger hydrogen bonding and the occurrence of a strong synergy. 相似文献
88.
89.
90.
Reversible aggregation of spheres is simulated using a novel method in which clusters of bound spheres diffuse collectively with a diffusion coefficient proportional to their radius. It is shown that the equilibrium state is the same as with other simulation techniques, but with the present method more realistic kinetics are obtained. The behavior as a function of volume fraction and interaction strength was tested for two different attraction ranges. The binodal and the percolation threshold were determined. The cluster structure and size distribution close to the percolation threshold were found to be consistent with the percolation model. Close to the binodal phase separation occurred through the growth of spherical dense domains, while for deep quenches a system spanning network is formed that coarsens with a rate that decreases with increasing attraction. We found no indication for arrest of the coarsening. 相似文献