手性络合物[M(bpy)_2(phen)]~(2+)和[M(phen)_2(bpy)]~(2+)(M=Ru,Os)圆二色谱的理论解析

应用密度泛函理论,在B3LYP/LanL2DZ水平上对C2对称性的混配络合物[M(bpy)2(phen)]2+和[M(phen)2(bpy)]2+(M=Ru、Os;bpy=2,2'-bipyridine;phen=1,10-phenanthroline)在水溶液中的几何构型进行了优化,并用TDDFT/B3LYP方法和相同的基组计算了其激发能、旋转强度和振子强度,绘制了相应的圆二色谱(CD).在分析有关跃迁性质的基础上,对实验圆二色谱的谱带进行了明确的解析和指认,同时讨论了短波区激子裂分的规律性.结果表明:四种络合物在长波区(λ>320nm)的CD吸收带主要是由d-π*跃迁产生的荷移谱带;短波区(λ<320nm)则是配体上平行于长轴的π-π*跃迁产生的激子耦合带,且对于Λ构型表现为正的手性激子裂分.其中,[M(bpy)2(phen)]2+只显示出正负两个激子带,分属于联吡啶和邻菲咯啉配体;而[M(phen)2(bpy)]2+则有三个激子带,其中左侧的两个(一负一正)属于邻菲咯啉配体,右侧的正带则属于联吡啶配体.此外,尽管激子耦合属于远程相互作用,但用TDDFT计算的激子裂分样式仍是正确的.这些结论对于深入理解有...     

由一个实例引发的对莫尔理论和双剪统一强度理论的改进

以某型火炮身管设计为例,采用双剪统一强度理论对火炮身管的壁厚进行了设计。然而,在火炮身管强度计算中得出了如下结论:当身管外径平方与内径平方之比小于1+b时,若材料的其它参数不变,材料的压缩屈服极限越大,其所能承受内压的能力越差,b为双剪统一强度理论中的参数。这是有悖常理的。针对该现象本文考虑各主应力的正负取值情况,对库伦—莫尔理论和双剪统一强度理论的改进问题进行了探讨。并应用改进的双剪统一强度理论再次计算,得到了满意的结果。     

Collision efficiency of two nanoparticles with different diameters in Brownian coagulation

The collision efficiency of two nanoparticles with different diameters in the Brownian coagulation is investigated. The collision equations are solved to obtain the collision efficiency for the dioctyl phthalate nanoparticle with the diameter changing from 100 nm to 750 nm in the presence of the van der Waals force and the elastic deformation force. It is found that the collision efficiency decreases as a whole with the increase of both the particle diameter and the radius ratio of two particles. There exists an abrupt increase in the collision efficiency when the particle diameter is equal to 550 nm. Finally, a new expression is presented for the collision efficiency of two nanoparticles with different diameters.     

Characteristic time scales of velocity and pressure events

Numerical and wind tunnel simulations of full-scale wind loads on structures are usually performed at a lower Reynolds number and different turbulence parameters. One way to assess the validity of such simulations is through matching magnitudes, duration and/or spectral characteristics of simulated pressure peaks with full-scale data. Because wavelet analysis provides a time/frequency decomposition, it has been proposed as an analysis tool for the intermittent and transient pressure peaks. This work aims at answering the question as to whether different wavelets yield the same-scale decomposition of pressure peaks and velocity events and could, thus, be used as a tool for the analysis of extreme loads on structures. The results show that, by isolating the peaks or events with a modified Gaussian window prior to applying the wavelet transform, the dependence of the measured time scale on different wavelet functions is reduced. The time scales of the pressure peak and the velocity event are estimated to be about the same indicating that one contributing factor, at the peak scale, to the pressure peak lies in the variation of the incoming flow at the same scale.     

Design of axisymmetric sandwich plates for alternative loads

The minimal-weight design of sandwich plates whose rigidplastic face sheets obey the Tresca yield condition and which are subjected to two alternative loads is systematically determined by the method of stress variation. It is shown that, when the loads are unidirectional, the general solution for a certain class of edge conditions consists of five fundamentally different designs. The totality of optimal design solutions is depicted in the form of a design chart. A comprehensive example is presented to illustrate the method.This paper is based in part upon a dissertation submitted by the first author to The University of Iowa in partial fulfillment of requirements for the PhD Degree.     

Thermodynamic characteristics of the activity of selected chromatographic sorbents

Summary The possibility of comparing various chromatographic sorbents in respect of their activity is discussed utilizing a simple thermodynamic approach presented earlier.     

Discrete-Time Geo X /G/1 Queue with Preemptive Repeat Different Priority

This paper considers a discrete-time Geo ^X /G/1 queue accepting two classes of messages with preemptive repeat different priority. Service times of messages of each priority class are i.i.d. according to a general discrete distribution function that may differ between two classes. The completion time and the stability condition for our system are investigated. By using the supplementary variable method and the generating function technique, we derive the joint system contents distributions at various observation instants and also compute the probability distribution for the unfinished work.     

Dynamic stiffness matrix of a general cable element

Summary A computational scheme for determining the dynamic stiffness coefficients of a linear, inclined, translating and viscously/hysteretically damped cable element is outlined. Also taken into account is the coupling between inplane transverse and longitudinal forms of cable vibration. The scheme is based on conversion of the governing set of quasistatic boundary value problems into a larger equivalent set of initial value problems, which are subsequently numerically integrated in a spatial domain using marching algorithms. Numerical results which bring out the nature of the dynamic stiffness coefficients are presented. A specific example of random vibration analysis of a long span cable subjected to earthquake support motions modeled as vector gaussian random processes is also discussed. The approach presented is versatile and capable of handling many complicating effects in cable dynamics in a unified manner.The work reported in this paper has been carried out as a part of a research project on dynamics of extensible cables funded by the Department of Science and Technology, Government of India. The financial support received is gratefully acknowledged.     

Retention time in series-coupled columns: An experimental investigation of the non-thermodynamic effects

A previously established model of a system of series-coupled columns is implemented for the experimental investigation of non-thermodynamic contributions to the retention time in systems of two series-coupled columns. The results show excellent agreement between theory and experiment and also stresses the importance of non-thermodynamic contributions to retention times.