Fe/Zn双金属氰化物催化剂催化环氧丙烷聚合的活性结构研究

以氯化锌、铁氰化钾（含有整合剂）的水溶液为原料，合成了铁锌双金属氰化物（DMC）催化剂。为获得高活性的DMC催化剂，需将叔丁醇 、多元醇螯合剂螯合至其结构中，用XRD、XPS等分析手段，对铁锌DMC催化剂的结构与活性进行分析表征。实验发现，DMC催化剂的晶体结构与螯合剂密切相关，螯合剂能显著降低DMC催化剂的结晶程度，从而提高DMC催化剂的活性。同时，氯化锌过量也有利于DMC催化剂活性的提高。并表征了相关DMC催化剂的活性中心。     

Static atomic displacements of Sn in disordered NiAs/Ni2In type HT-Ni1+δSn

The crystal structures of the intermediate solid solution HT (high temperature) Ni_1+δSn with δ=0.28, 0.52 and 0.61 (refined Ni contents) have been analyzed in detail by X-ray diffraction on single crystals. The previously reported basic atomic arrangement, i.e., a NiAs/Ni₂In structure type (P6₃/mmc, Ni(1) on 2a, 0 0 0, Ni(2) with an occupancy δ on 2d, and Sn on 2c, ), is confirmed. However, strong anisotropic atomic displacements occur for Sn within the a-b plane of the hexagonal unit cell, which require a Gram-Charlier expansion of the probability density function of Sn in order to obtain a good fit to the diffraction data. Direction, magnitude and the concentration dependence of the displacements can be interpreted in terms of the geometrical requirements of the different local atomic configurations in the planes z=±1/4, so that the displacements can be identified as static ones.     

Local polarizabilities in molecules,based on ab initio Hartree-Fock calculations

A method to separate the total molecular polarizability, calculated in the uncoupled Hartree-Fock approximations, into local contributions is proposed. The method is tested for H₂, H₂O, H₂CO and C₆H₆ and the results are discussed. It is found that the ratio of the polarizability contributions for two atoms in a molecule almost only depends on the type of atoms and is almost independant of molecule.     

Weighted local polynomial estimations of a non-parametric function with censoring indicators missing at random and their applications

In this paper, we consider the weighted local polynomial calibration estimation and imputation estimation of a non-parametric function when the data are right censored and the censoring indicators are missing at random, and establish the asymptotic normality of these estimators. As their applications, we derive the weighted local linear calibration estimators and imputation estimations of the conditional distribution function, the conditional density function and the conditional quantile function, and investigate the asymptotic normality of these estimators. Finally, the simulation studies are conducted to illustrate the finite sample performance of the estimators.     

Realization of fixed point sets

Letf:XX be a selfmap of a compact connected polyhedron, andA a nonempty closed subset ofX. In this paper, we shall deal with the question whether or not there is a mapg:XX homotopic tof such that the fixed point set Fixg ofg equalsA. We introduce a necessary condition for the existence of such a mapg. It is shown that this condition is easy to check, and hence some sufficient conditions are obtained.Partially supported by the Natural Science Foundation of Liaoning University.     

Multi-element Saha–Boltzmann and Boltzmann plots in laser-induced plasmas

A multi-element Saha–Boltzmann plot method is proposed for the determination of the temperature and the relative number density in laser-induced plasmas, assuming local thermodynamic equilibrium and stoichiometry conservation. The method has been applied to the characterization of a plasma generated with a Cu–Fe–Ni–Mn alloy, using a Nd:YAG laser in air at atmospheric pressure. Spectra of the local emissivity have been obtained by spatial deconvolution of the intensity spectra, obtained with spatial resolution. Saha–Boltzmann plots obtained from the emissivities of 58 spectral lines of Fe I, Fe II, Ni I, Ni II, Mn I and Mn II have been fitted to linear behavior with high correlation, which shows the validity of the equation proposed. Radial distributions of the temperature and number densities of neutral atoms and ions have been determined. The results obtained reinforce the initial considerations of local thermodynamic equilibrium and conservation of stoichiometry. The proposed equation can also be applied to only one ionization species (multi-element Boltzmann plot). Spatially-integrated measurements of the plasma emission have also been performed to show that, in this case, the application of the method to the line intensities provides the two different apparent temperatures for neutral atoms and ions.     

Electron correlation effects on the shape of the Kohn–Sham molecular orbital

Even systems in which strong electron correlation effects are present, such as the large near-degeneracy correlation in a dissociating electron pair bond exemplified by stretched H₂, are represented in the Kohn–Sham (KS) model of non-interacting electrons by a determinantal wavefunction built from the KS molecular orbitals. As a contribution to the discussion on the status and meaning of the KS orbitals we investigate, for the prototype system of H₂ at large bond distance, and also for a one-dimensional molecular model, how the electron correlation effects show up in the shape of the KS σ _g orbital. KS orbitals φ^HL and φ^FCI obtained from the correlated Heitler-London and full configuration interaction wavefunctions are compared to the orbital φ^LCAO, the traditional linear combination of atomic orbitals (LCAO) form of the (approximate) Hartree-Fock orbital. Electron correlation manifests itself in an essentially non-LCAO structure of the KS orbitals φ^HL and φ^FCI around the bond midpoint, which shows up particularly clearly in the Laplacian of the KS orbital. There are corresponding features in the kinetic energy density t _s of the KS system (a well around the bond midpoint) and in the one-electron KS potential v _s (a peak). The KS features are lacking in the Hartree-Fock orbital, in a minimal LCAO approximation as well as in the exact one. Received: 11 December 1996 / Accepted: 10 January 1997     

EPR parameters and local geometry for Cr3+ and V2+ ions in HfS2 crystals

From the high-order perturbation formulas of EPR parameters (zero-field splitting D, g factors gparallel, gperpendicular and hyperfine structure constants Aparallel, Aperpendicular) based on the two spin-orbit coupling parameter model for 3d3 ions in trigonal symmetry, the EPR parameters of Cr3+ and V2+ ions in HfS2 crystals are calculated. From the calculations, it is found that the local trigonal distortion angle theta of impurity center in HfS2:Cr3+ is smaller than that in HfS2:V2+. The dominant cause of the small zero-field splitting |D| and g-anisotropy |Deltag|=|gparallel-gperpendicular| in HfS2:Cr3+ (compound to HfS2:V2+) is due to the small local trigonal distortion angle theta rather than to the small impurity-ligand distance R in HfS2:Cr3+.     

On the use of local basis sets for localized molecular orbitals

Two procedures are discussed for the direct variational optimization of localized molecular orbitals which are expanded in local subsets of the molecular basis set. It is shown that a Newton-Raphson approach is more efficient than an iterative diagonalization scheme. The effect of the basis-set truncation on the quality ofab-initio SCF results is investigated for Be, Li₂, HF, H₂O, NH₃, CH₄ and C₂H₆.