The mechanism of ethylene polymerization by nickel salicylaldiminato catalysts - Agostic interactions and their kinetic isotope effects

The ethylene polymerization reaction of a neutral nickel catalyst was studied by DFT calculations at the Becke3LYP/6-31G(d) level of theory. As in related cases a β-agostic bond stabilizes the nickel alkyl ground states. Transition states for the insertion of the olefin show a distinct α-agostic interaction, which has not been observed for late metal polymerization catalysts before. An ethylene-alkyl complex was identified as the resting state of the reaction. The overall barrier height of the reaction amounts to 17.54 kcal/mol, which slightly increases to 17.60 kcal/mol for the polymerization of deuterated ethylene. Therefore, a small positive kinetic isotope effect (k_H/k_D = 1.09) can be calculated, which is caused by the α-agostic interaction in the transition state. A comparison to other late metal based polymerization systems reveals that the ethylene coordination step of highly active catalysts is significantly lower in energy compared to catalysts which are only moderately active.     

Effective magnetic properties of a composite material with circular conductive elements

Effective magnetic properties of a composite meta-material consisting of periodically arranged circular conductive elements are studied theoretically. A general expression for the effective bulk permeability is obtained with mutual effects and lattice ordering being taken into account. The resonance frequency of the permeability is found to be strongly dependent on the size and shape of the unit cell. Frequency dispersion of the permeability is studied with special attention paid to the frequency range, where negative values of the permeability are possible. Corresponding recommendations for optimisation of the meta-materials with negative permeability are made. The results are confirmed by numerical simulations of the finite structure behaviour in an external magnetic field. Received 19 April 2002 Published online 31 July 2002     

有限时滞微分系统依照双测度的实际稳定性

本文对具有有限时滞的泛函微分方程建立了关于依照两种测度的实际稳定性的Razumikhin型判定定理，其中未采用通常的辅助函数，且可运用多个含有状态变量x的部分变元的Lyapunov函数，得出部分变远实际稳定性的判定定理，从而改进了已有的结果。     

Space time-index plots for probing dynamical nonstationarity

We propose a simple method to efficiently probe dynamical nonstationarity in observed time series. In a space time-index plot, the density distributions as a function of normalized time-index are V-shaped due to nonstationarity. We show that this method is workable for short data sets and typical examples are illustrated.     

Chemical reactivity of hypervalent silicon compounds: The local hard and soft acids and bases principle viewpoint

The silicon atom may increase its coordination number to values greater than four, to form pentacoordinated compounds. It has been observed experimentally that, in general, pentacoordinated compounds show greater reactivity than tetracoordinated compounds. In this work, density functional theory is used to calculate the global softness and the condensed softness of the silicon atom for SiH _n F_4−n and SiH _n F _5−n ¹⁻ . The values obtained show that the global and condensed softness are greater in the pentacoordinated compounds than in the tetracoordinated compounds, a result that explains the enhanced reactivity. If the results are analysed through a local version of the hard and soft acids and bases principle, it is possible to suggest that in nucleophilic substitution reactions, soft nucleophiles preferably react with SiH _n F _5−n ¹⁻ , and hard nucleophiles with SiH _n F_4−n .     

含色散介质的一维光子晶体微腔的透射谱

研究了含色散介质的一维光子晶体微腔的透射谱,对色散介质采用Lorentz振子模型,腔模的频率设置在光子晶体带隙中心。发现当吸收可以忽略时,色散效应将导致在腔模附近有很高的态密度,与此相应地在透射谱中出现一个较宽的透射带。当吸收存在时透射带中心的透射峰消失,但带尾的透射峰依然存在。     

Coverage dependent magnetic properties of Co chain-coated carbon nanotube

Magnetic properties of Co chain-coated carbon nanotube (CNT) were investigated using a first-principles calculation. Binding energy between Co chain and CNT increased with the coverage ratio, and the adsorption of Co chains on CNT enhanced the conductance channel. Total magnetic moment of Co chains coated on CNT increased with the coverage ratio, while the magnetic moment per Co atom decreased due to spin flip of majority spin states in Co atoms. Spin polarization at the Fermi level of the Co chains was calculated to converge to that of bulk fcc Co.     

Barrier-free intermolecular proton transfer in the uracil-glycine complex induced by excess electron attachment

The photoelectron spectra (PES) of anions of uracil-glycine and uracil-phenylalanine complexes reveal broad features with maxima at 1.8 and 2.0 eV. The results of ab initio density functional B3LYP and second order M?ller-Plesset theory calculations indicate that the excess electron occupies a π^* orbital localized on uracil. The excess electron attachment to the complex can induce a barrier-free proton transfer (BFPT) from the carboxylic group of glycine to the O8 atom of uracil. As a result, the four most stable structures of the anion of uracil-glycine complex can be characterized as the neutral radical of hydrogenated uracil solvated by the anion of deprotonated glycine. The similarity between the PES spectra for the uracil complexes with glycine and phenylalanine suggests that the BFPT is also operative in the case of the latter anionic species. The BFPT to the O8 atom of uracil may be related to the damage of nucleic acid bases by low energy electrons because the O8 atom is involved in a hydrogen bond with adenine in the standard Watson-Crick pairing scheme. Received 6 April 2002 Published online 13 September 2002     

Vibrational EELS and DFT study of propionic acid and pyruvic acid on Ni(1 0 0): Effects of keto group substitution on room-temperature adsorption and thermal chemistry

The room-temperature adsorption and thermally induced processes of propionic acid and pyruvic acid on Ni(1 0 0) have been investigated by electron energy loss spectroscopy (EELS). Computational vibrational analysis of the optimized bidentate structures for acid-Ni model complexes (involving the organic acid and a Ni atom) has been performed by using the two-layer ONIOM method with the Density Functional Theory and used to interpret the vibrational EELS data. Dehydrogenation of the hydroxyl group is found to result in bonding of the carboxylate group in the propionate and pyruvate adspecies to either a single Ni surface atom in a bidentate configuration or two neighbouring Ni atoms in a bridge configuration. Given the similarities in the total energies and related vibrational frequencies obtained by the calculations in the case of pyruvate adspecies, it is difficult to differentiate the alternate adsorption structure, in which the keto O and hydroxyl O atoms are bonded to a Ni atom in a five-member chelate ring configuration. Furthermore, temperature-dependent EELS studies show that both the propionate and pyruvate adspecies could decompose upon annealing to above 400 K and further dissociate to CO adspecies above 550 K and to C and/or O above 600 K.     

Effect of external Gaussian random field on phonon spectrum of linear atomic chains

We present the theoretical study of the effect of external random field characterized by a Gaussian probability distribution function on the continuous phonon spectrum of one-dimensional (1D) chain, based on the Jacobian matrix method. The cumulative effect of the random field and simple isotopic defect is studied analytically and numerically. The Gaussian random field removes a square-root divergence appearing in the phonon spectrum of ideal 1D chain. The impurity phonon DOS shows strong dependence on the variance and the mean of the random field and exhibits very different behavior from the non-random case: the continuous spectrum is expanded and the δ-peak, describing discrete impurity vibrations in the non-random chain with the impurity, falls into a continuous zone.