On the theory of radiative transitions in centrosymmetric complexes

The theory of radiative transitions, in centrosymmetric complexes, is examined in great detail, within the framework of the crystal field method.In connection with radiative transitions, the current method of calculations, with and without invoking closure approximation, are considered from a purely theoretical point of view, by taking advantage of the irreducible tensor method put forward by Griffith.Explicit equations are derived throughout the course of this work to account for the vibronic electric dipole moments, associated with d-d and f-f type of excitations.At high Academy of Pedagogic Sciences, Santiago, Chile.     

Phase-fixed double-group 3-Γ symbols. IV. Real 3-Γ symbols and coupling coefficients for the group hierarchies T* ⊃ C 3 * and T* ⊃ C 2 *

We present sets of real 3- symbols which correspond to explicitly given irreducible matrix representations for the two double group hierarchies T* C ₃ ^* and T* C ₂ ^* . They fit into the formalism exposed in a previous paper [1] on the general theory of 3- symbols and coupling coefficients and illustrate much of the discussion in a subsequent one [2] treating the particular properties of the double groups.     

Vibronisches Spektralverhalten von Molekülen: XX. Theoretische Untersuchung der S2←S0-Absorption des Pyrens im Rahmen der Herzberg-Teller-Näherung erster Ordnung

Summary On the basis of the completely-optimized S₀ and S₂ molecular geometries of pyrene the vibrational structure of the electronic S₂S₀ transition was calculated within both the Condon approach and the first-order Herzberg-Teller approach. The theoretical results demonstrate the significant influence of vibronic coupling. An analysis of the active vibrational modes is given. The theory-experiment comparison within the Herzberg-Teller approach is satisfactory.

     

N_2-DART-Orbitrap中的特征气相离子反应及在西药快速检测中的应用

采用实时直接分析(DART)离子源串联高分辨质谱Orbitrap技术(DART-Orbitrap MS),对8种市售常见西药进行有效成分分析,建立了一种快速、简便、准确测定西药中有效成分的方法.对DART离子源的离子化温度、扫描模式、操作气体种类、辅助溶剂种类及其酸碱性等实验条件进行了优化,得到最佳实验条件.实验结果表明,正谱条件下,采用N_2气作为操作气体时,待测组分准分子离子峰[M+H]+同样具有较高的灵敏度和谱图辨识度.因此,N2气可以替代昂贵的He气作为DART离子源的操作气体用于8种药物有效成分的现场实时检测.该方法具备成本低、快速和操作简便的特点.通过分析待测组分的特征碎片离子,发现了N2-DART离子源中的特征离子反应,包括氧化反应和重排反应.根据获得的特征碎片离子对N_2-DART-MS中发生的反应机理进行推导,并结合理论计算对其进行验证.N_2-DART-MS技术有望应用于复杂基质混合物的现场快速检测中.     

Novel filled polymer composites prepared from in situ polymerization via a colloidal approach: II. Blends of kaolin/Nylon-6 in situ composites with conventional Nylon-6 and -66

A novel in situ composite comprised of kaolin clay fillers and polyamide 6 (Nylon-6) was synthesized via a colloidal approach by suspending kaolin particles in aqueous caprolactam and then polymerizing the caprolactam under elevated temperature and pressure. This in situ polymerization technique enables the deposition of nylon molecules directly onto the filler surface. It offers a much larger contact surface area for the nylon molecules to interact with the filler particles and enhances filler/matrix interaction through polymer miscibility. The kaolin particles were shown to be uniformly dispersed in Nylon-6 matrix without appreciable agglomeration. In the highly clay-loaded composites such as the 50/50 kaolin/Nylon-6 in situ composite, the deposited nylon molecules probably form a coated layer on the filler particles. This kind of nylon coated fillers may be applied as a reinforcing entity to commercial Nylon-6 or −;66 by improving particle dispersion and melt processability. The 50/50 kaolin/Nylon-6 in situ composites have been used as a masterbatch for blending with commercial Nylon-6 and Nylon-66 to take advantage of their good properties and to reduce cost. Rheology and mechanical properties of the masterbatch/nylon composites have been investigated in comparison with those of the conventional melt-mixed composites. The improvement of rheological and mechanical properties of the in situ composites has been discussed in relation to the composite structure. © 1996 John Wiley & Sons, Inc.     

Envelopes of splines in the projective plane

In this paper a family of curves—Riemannian cubics—inthe unit sphere and the real projective plane is investigated.Riemannian cubics naturally arise as solutions to variationalproblems in Riemannian spaces. It is remarkable to find thatan envelope of lines generated by a Riemannian cubic in onespace is (nearly) a Riemannian cubic in another space.     

Inelastic partial cross sections for scattering of HF by neon

An analytic expression of the potential energy surface (PES) of the ground state of the Ne-HF complex is obtained by utilizing nonlinear least square method to fit the intermolecular interaction energies [Zhang Y. Guizhou Science, 2003, 21(3): 9–13 (in Chinese)], which have been computed using the augmented correlation-consistent polarized quadruple zeta basis set aug-cc-pVQZ at the theoretical level of CCSD (T). On the basis of the PES, the partial cross sections (PCSs) at the incident energies of 60, 75, 100 and 150 meV for collisions between Ne atoms and HF molecules are calculated using the quantum close coupling approach. The effects of the long-range attractive and the short-range anisotropic interactions on the inelastic PCSs are discussed in detail. The results show: (1) The long-range attractive well of the EPS makes the significant contribution to the lower excitation PCSs, especially the tail maximum for j = 0→j′ = 1 transitions, whereas no contribution is to the j′⩾3 inelastic transitions. (2) The short-range (the repulsive and attractive) interaction makes the significant contribution to the lower excitation PCSs, especially the main peak for j = 0→j′ = 1, 2. As for the transitions of j′⩾3, the short-range interaction plays a key role in the inelastic excitation. (3) Although the positions of the maximums and minimums of the inelastic PCSs are different at the collision energies, they correspond to almost the same impact parameter. Supported by the National Natural Science Foundation of China (Grant Nos. 10676025 and 10574096)     

Existence of solutions for a nonlinear system with a parameter

In this paper, the existence of solutions for a system of nonlinear equations is considered. n² nonzero real solutions are obtained by using the critical point theory. Additionally, the Dirichlet boundary value problems of even order difference equations and partial difference equations are investigated.     

Multicriteria analysis in decision making under information uncertainty

This paper presents results of research related to multicriteria decision making under information uncertainty. The Bellman–Zadeh approach to decision making in a fuzzy environment is utilized for analyzing multicriteria optimization models (X,M models) under deterministic information. Its application conforms to the principle of guaranteed result and provides constructive lines in obtaining harmonious solutions on the basis of analyzing associated maxmin problems. This circumstance permits one to generalize the classic approach to considering the uncertainty of quantitative information (based on constructing and analyzing payoff matrices reflecting effects which can be obtained for different combinations of solution alternatives and the so-called states of nature) in monocriteria decision making to multicriteria problems. Considering that the uncertainty of information can produce considerable decision uncertainty regions, the resolving capacity of this generalization does not always permit one to obtain unique solutions. Taking this into account, a proposed general scheme of multicriteria decision making under information uncertainty also includes the construction and analysis of the so-called X,R models (which contain fuzzy preference relations as criteria of optimality) as a means for the subsequent contraction of the decision uncertainty regions. The paper results are of a universal character and are illustrated by a simple example.     

Adsorbents and columns in analytical high-performance liquid chromatography: a perspective with regard to development and understanding

A brief historical survey is presented on the evaluation of silica adsorbents in analytical HPLC. The theory of analytical HPLC is mostly still being based on the height equivalent to a theoretical plate concept and the van Deemter equation that was derived from gas phase adsorption involving a linear adsorption isotherm and fast mass transfer kinetics. One can obviously wonder whether the use of the van Deemter equation is relevant and valid for the evaluation of the performance of HPLC systems, where most often the liquid solutes involve charged molecules in electrolytes and in very many cases the adsorbates are macromolecules having diffusion coefficients of small magnitude. Instead of the van Deemter equation, a multi-scale modelling approach that involves microscopic and macroscopic dynamic non-linear mass-transfer-rate models should be employed. Furthermore, advanced experimental methods for the characterisation of porous media and the distribution of the density of immobilised active sites (e.g., ligands) on surfaces as well as microscopic pore-network modelling and molecular dynamics modelling and simulation methods could be used for the design of novel adsorbents whose porous structures and immobilised active sites would provide effective mass transport and adsorption rates for realising efficient separations as well as high dynamic capacities when larger throughputs are required.