Nature of "hydrogen bond" in the diborane-benzene complex: covalent, electrostatic, or dispersive?

Motivated by the recent discovery of unusual "hydrogen bonding"-like interaction between a borane system and benzene molecules in a molecular crystal, we carried out quantum mechanical calculations on a model complex, diborane-benzene cluster. The aim is to understand the nature of this unique interaction, which is expected to play an essential role in this novel class of molecular crystals. As analyzed in the present study, the interaction between diborane and benzene is special in the following aspects: (1) this interaction is mostly dispersive; (2) the observed pseudodirectionality with one of the diborane bridge hydrogen directed toward the benzene centroid minimizes the van der Waals contact; and (3) in the "hydrogen bond" map, this interaction is located in a unique region, which is presently populated by a few known molecular complexes with very different chemical characteristics. It is anticipated that the results from the present analysis will provide meaningful guidance for molecular engineering with diborane-benzene as a building block and for stabilization of this and possible other hydrogen bonds by dispersive contributions.     

Synergistic approach to improve "alchemical" free energy calculation in rugged energy surface

The authors present an integrated approach to "alchemical" free energy simulation, which permits efficient calculation of the free energy difference on rugged energy surface. The method is designed to obtain efficient canonical sampling for rapid free energy convergence. The proposal is motivated by the insight that both the exchange efficiency in the presently designed dual-topology alchemical Hamiltonian replica exchange method (HREM), and the confidence of the free energy determination using the overlap histogramming method, depend on the same criterion, viz., the overlaps of the energy difference histograms between all pairs of neighboring states. Hence, integrating these two techniques can produce a joint solution to the problems of the free energy convergence and conformational sampling in the free energy simulations, in which lambda parameter plays two roles to simultaneously facilitate the conformational sampling and improve the phase space overlap for the free energy determination. Specifically, in contrast with other alchemical HREM based free energy simulation methods, the dual-topology approach can ensure robust conformational sampling. Due to these features (a synergistic solution to the free energy convergence and canonical sampling, and the improvement of the sampling efficiency with the dual-topology treatment), the present approach, as demonstrated in the model studies of the authors, is highly efficient in obtaining accurate free energy differences, especially for the systems with rough energy landscapes.     

Essential energy space random walk via energy space metadynamics method to accelerate molecular dynamics simulations

To overcome the possible pseudoergodicity problem, molecular dynamic simulation can be accelerated via the realization of an energy space random walk. To achieve this, a biased free energy function (BFEF) needs to be priori obtained. Although the quality of BFEF is essential for sampling efficiency, its generation is usually tedious and nontrivial. In this work, we present an energy space metadynamics algorithm to efficiently and robustly obtain BFEFs. Moreover, in order to deal with the associated diffusion sampling problem caused by the random walk in the total energy space, the idea in the original umbrella sampling method is generalized to be the random walk in the essential energy space, which only includes the energy terms determining the conformation of a region of interest. This essential energy space generalization allows the realization of efficient localized enhanced sampling and also offers the possibility of further sampling efficiency improvement when high frequency energy terms irrelevant to the target events are free of activation. The energy space metadynamics method and its generalization in the essential energy space for the molecular dynamics acceleration are demonstrated in the simulation of a pentanelike system, the blocked alanine dipeptide model, and the leucine model.     

热致性共聚酯液晶的研究——以双酚-对苯二甲酸酯为间隔段

热致性共聚酯液晶由于具有优异的热、机械及加工等性能,引起人们对其应用及基础研究的重视。本实验室曾对以不同长度碳链为软间隔段的共聚酯进行了研究,在产物介晶单元含量不高(约20％)时即可表现出明显液晶性。本文选用以双酚A(BPA)或双酚S(BPS)-对苯二甲酸酯为间隔段进行了研究。     

几种光学图象相位加密方法的比较

本文分析比较了多种实现光学图象相位加密的方法,发现不同方法获得的加密图象有不同类型的噪音分布.无论加密相位是随机相位模板、浑沌序列的相位列阵,还是用相位重构迭代算法计算的结果,它们都能起到加密图象的功能.解密图象的质量或被相关识别的能力与解密过程中所使用正确解密相位的不同部分以及高低频分量多少有关,且其依赖程度是由不同的加密方法自身决定.     

一种液晶共聚酯/粘土纳米复合材料的制备及其相转变温度

一些无机微粒被广泛用做聚合物的增强材料,其中特别引起人们注意的是一种粘土,即蒙脱土（ｍｏｎｔｍｏｒｉｌｌｏｎｉｔｅ）．蒙脱土具有层状结构,其特点一是微粒尺寸小,二是可以和多种单体发生插层聚合反应,给出聚合物／蒙脱土纳米复合材料［１～３］．纳米复合材料指的是其基质中分散相的尺寸至少有一维小于１００ｎｍ数量级的复合材料．由于其纳米尺度效应、大的比表面积以及强的界面相互作用,纳米复合材料的物理力学性能优于相同组分常规复合材料．因此,无论从基本理论研究角度还是从应用角度上看,对聚合物纳米复合材料的研究都…     

杂多酸引发四氢呋喃聚合反应 Ⅱ.水的反应行为

前报我们对低腐蚀性非均相的磷钨杂多酸Ｈ３ＰＷ１２Ｏ４０（ＰＷ１２）引发体系进行了研究［１］,发现环氧乙烷（ＥＯ）可有效地促进ＰＷ１２引发的四氢呋喃（ＴＨＦ）聚合反应,大幅度地降低了引发剂用量,聚合物收率显著提高,并发现聚合过程中不存在链终止反应．产物...     

"Ljung"型随机算法的收敛性

本文研究了“Ｌｊｕｎｇ”算法的收敛条件,给出了两类条件下的收敛定理,并将收敛定理推广到观察值更复杂的情形     

光诱导转化法制备单晶Ag纳米三棱体和立方体

The preparation of Ag nanoparticles with the non-spherical shape has been conducted from aqueous solution by photo induced conversion. Ag nanoprisms (80～120nm) and nanocube s(90～200nm) were respectively obtained in the presence of trisodiumcitrate (TSC) orpolyvinylpirrolidon (PVP). These Ag nanoparticles were single-crystals. The results showed that Ag nanoprisms had apreferential growth direction along the Ag(111) axis and Ag nanocubes had a preferential growth direction along the Ag(100) axis. By means of characterization with TEM, ED and UV-V is Spectra, the fundamental analyses and discussion about the changing causes of nanoparticles shape from spherical tonon-spherical have been carried out in the photo induced process.     

基于非齐次泊松过程的共享停车场运营策略

为缓解因城市某些地区、某些时间段停车供需不平衡的问题,将居住区内空闲车位进行共享的解决方法已引起多方的关注。在居住区实施共享停车时,需考虑车位提供者与社会停车用户的时空冲突问题。本文首先基于实际停车行为数据,假设车位提供者返回过程呈非齐次泊松过程;其次,以居住区共享停车为运营场景,居住区停车场车位共享率和管理者收益最大化为目标,构建了相应的数学优化模型;最后,设计了粒子群求解算法,通过数值实验,分析该场景下的最优运营策略。结果表明：(1)社会停车用户的最大离开速率在其占车位总数的四分之一左右时,管理者总收益最大;(2)随着车位提供者车位返回速率突变时间的改变,要使得总收益及车位共享率最优,第一阶段变更共享策略时间设置在车位提供者返回速率突变时间前三十分钟内,第二阶段变更共享策略时间应设置在车位提供者返回速率突变时间后一小时五十分钟以内为宜。