In view of immense importance of silylenes and the fact that their properties undergo significant changes on substitution with halogens, here, we have used B3LYP/6-311++G** level of theory to access the effects of 1–4 halogens (X = F, Cl, Br, and I) on four unprecedented sets of cyclopentasilylene-2,4-dienes; with the following formulas: SiC4H3X ( 1 X ), SiC4H2X2 ( 2 X ), SiC4HX3 ( 3 X ), and SiC4X4 ( 4 X ). In going down from F to I, the singlet (s)-triplet (t) energy gap (ΔEs-t, a possible indication of stability), and band gap (ΔEH-L) decrease while nucleophilicity (N), chemical potential (μ), and proton affinity (PA) increase. The overall order of N, μ, and PA for each X is 2 X > 1 X > 3 X > 4 X . Precedence of 2 X over 1 X is attributed to the symmetric cross conjugation in the former. The highest and lowest N are shown by 2 I and 4 F . The trend of divalent angle () for each X is 4 X > 1 X > 3 X > 2 X . The results show that in going from electron withdrawing groups (EWGs) to electron donating groups (EDGs), the ΔEs-t and ΔEH-L decrease while N, μ, and PA increase. Also, rather high N of our scrutinized silylenes may suggest new promising ligands in organometallic chemistry. 相似文献
The γcmc values of CTAB-SDS decrease from 63.67 mN/m at 10‡C to 36.38 mN/m at 90‡C, slightly lower than those of either CTAB or SDS.
Correspondingly, the CMC of CTAB-SDS decreases almost by half. The increase of surface activity of CTAB-SDS can be attributed
to the relatively weak electrostatic interaction at high temperature, which is supported by the increase of solubility of
CTAB-SDS with rise in temperature. Catalytic effect on oxidation of toluene derivatives with potassium permanganate follows
the order CTAB-SDS > SDS > CTAB. This is not caused by the dissociative effect of CTAB-SDS with low surface activity at low
temperature, as seen from the fact that almost all oxidative products can be retrieved for different toluene derivatives and
surfactants by mimicking the conditions of reaction. In the emulsifications of toluene derivatives at 90‡C, the time that
turbid water layers of surfactant solutions take to become clear is the same as that of the catalytic effect on oxidation
of toluene derivatives. Thus, it can be inferred that surfactants can improve the oxidation yields of toluene derivatives
by increasing the contact between two reacting phases. 相似文献
Palladium and molybdenum polycrystalline layers (clusters) have been deposited in a stainless steel UHV system onto a layer of alumina (Al2O3). This layer has been prepared by high temperature oxidation of an aluminium layer. The interaction of this system with nitrogen has been investigated at room temperature by an FEM technique. Under these conditions nitrogen spillover from molybdenum to palladium has been observed. 相似文献
A simple method is introduced to improve the analysing accuracy of circular groove guide. With this method, the characteristic equation of circular groove guide is derived and its solution is given and discussed.The Project Supported by National Natural Science Foundation of P.R.China 相似文献
The theory of tree-growing (RECPAM approach) is developed for outcome variables which are distributed as the canonical exponential family. The general RECPAM approach (consisting of three steps: recursive partition, pruning and amalgamation), is reviewed. This is seen as constructing a partition with maximal information content about a parameter to be predicted, followed by simplification by the elimination of ‘negligible’ information. The measure of information is defined for an exponential family outcome as a deviance difference, and appropriate modifications of pruning and amalgamation rules are discussed. It is further shown how the proposed approach makes it possible to develop tree-growing for situations usually treated by generalized linear models (GLIM). In particular, Poisson and logistic regression can be tree-structured. Moreover, censored survival data can be treated, as in GLIM, by observing a formal equivalence of the likelihood under random censoring and an appropriate Poisson model. Three examples are given of application to Poisson, binary and censored survival data. 相似文献
Supposa that f(x) is a quasidifferentiable function, defined on S(?)R~n where S is an open set, with a -equivalent bounded quasidifferential subfam ily. Lenma I 相似文献
The solar wind almost disappeared on May 11, 1999: the solar wind plasma density and dynamic pressure were less than 1cm−3 and 0.1 nPa respectively, while the interplanetary magnetic field was northward. The polar ionospheric data observed by the multi-instruments at Zhongshan Station in Antarctica on such special event day was compared with those of the control day (May 14). It was shown that geomagnetic activity was very quiet on May 11 at Zhongshan. The magnetic pulsation, which usually occurred at about magnetic noon, did not appear. The ionosphere was steady and stratified, and the F2 layer spread very little. The critical frequency of day-side F2 layer, f0F2, was larger than that of control day, and the peak of f0F2 appeared 2 hours earlier. The ionospheric drift velocity was less than usual. There were intensive auroral Es appearing at magnetic noon. All this indicates that the polar ionosphere was extremely quiet and geomagnetic field was much more dipolar on May 11. There were some signatures of auroral substorm before midnight, such as the negative deviation of the geomagnetic H component, accompanied with auroral Es and weak Pc3 pulsation.