稳态时剪应力作用下胶体簇团形成/破裂的机理

Population correlation function P(t) has been used to examine the mechanism of breakage and coalescence of clusters at steady-state under shear, the results are in qualitative agreement with experiments. The research indicates that with a weak potential the mechanism of breakage and coalescence of clusters at steady-state under shear is predominately controlled by the particle-particle model, but that with a strong potential the mechanism shifts to that of cluster-cluster for large clusters; for small clusters, however, the mechanism of particle-particle model seems still to remain predominate, further work needs to be done.     

胶体颗粒大小的分布——Ⅱ.物理显影中胶体催化剂颗粒大小的分布函数

本文用对数正态分布对物理显影中常用的Au、Ag及Ag_2s胶体催化剂的颗粒大小的实验分布进行了拟合。理论分布与实验分布的比较表明:本实验条件下制备的十二组胶体溶液其颗粒大小都服从了对数正态分布,并且不依赖于胶体的组成、大小及制备方法。因此,它们很可能遵从了同样的成核成长规律。     

胶体化学中计算机模拟的进展

简述了当前计算机模拟在胶体化学中的主要应用，特别涉及到数值方法的改进，热力学性质的模拟，簇团形成或破裂的动力学性质的模拟以及簇团结构和形貌特征的模拟。基本揭示了当前计算机模拟在胶体化学中的主要应用和最新进展。     

稳态时剪应力作用下肢体簇团形成/破裂的机理

胶体簇团形成／破裂过程机理研究一直是胶体研究中一个十分活跃的领域．因为不同的聚团机理导致胶体不同的物理化学性质：粘度、空隙度、导电性甚至光学特性等,因而使其备受注目．当前,实验研究证明了簇团边缘的胶体颗粒和介质有着频繁的交换’‘’,特别是在受到外力的作用下,这种交换会更加激烈．计算机模拟研究证实了簇团和介质间颗粒交换的机理可以是颗粒一颗粒型的,也可以是簇团一簇团型的”、”．所谓颗粒一颗粒型机理是指（接近或完全）由单个颗粒互相结合,或单个颗粒被结合进大的簇团．在结合期间,被结合的颗粒可以在簇团边缘…     

流体力学半径对估算胶体微球聚集速率常数的影响

胶体粒子聚集速率常数实验值远低于理论值一直是被普遍关注的问题.聚集速率常数的理论推导是基于粒子的几何半径来考虑的,但决定粒子扩散速率及聚集速率的应该是粒子的流体力学半径(大于几何半径),因而它是使聚集速率常数实验值低于理论值的因素之一.影响流体力学半径的因素很多,其中,带电粒子在溶液中因表面存在双电层,会明显增大流体力学半径,造成聚集速率减慢.而双电层的厚度又随溶液中离子强度的不同而改变.本工作在聚集速率的公式中引入了修正因子,即几何半径与其流体力学半径之比,以修正由于用几何半径代替流体力学半径带来的误差.其中几何半径和流体力学半径可以分别用扫描电镜(SEM)和动态光散射(DLS)来测定.以两种粒径的聚苯乙烯带电微球为例,考察了在不同离子强度下,该误差的大小.结果发现,对于半径为30 nm的微球,用流体力学半径计算的慢聚集速率常数比理论值偏低约8%.该误差随离子强度增加而减少.对于快聚集情况,流体力学半径对聚集速率基本没有影响.     

重力场和电解质浓度对胶体凝聚体分形结构的影响

运用李航等提出的新方法, 克服了DLVO理论中无法理论计算不同电解质浓度下颗粒的表面电位这一困难, 从而可以直接计算出不同电解质浓度下胶体颗粒间的位能. 同时, 还运用胶体颗粒动能的玻耳兹曼分布原理和蒙特卡罗方法来模拟胶体的运动, 并采用非弹性碰撞理论解决了碰撞后凝聚的有效概率问题. 在改进DDA模型的基础上, 成功地建立了以往的模拟中未能建立的重力场中电解质浓度与碰撞凝聚概率间的联系, 结果发现, (1)重力场作用下的凝聚体分形维数随电解质浓度变化的曲线完全不同于无重力条件下的曲线. 无重力作用下, 凝聚结构体分形维数随电解质浓度的变化比较缓慢, 曲线呈“L”形；而重力作用下的分形维数则呈明显的“S”形曲线. (2) 在重力条件下, 慢凝聚包括两个区域, 对电解质浓度不敏感区域和敏感区域. 在敏感区域存在一个电解质浓度的拐点. (3)无重力条件下,不同大小的胶体颗粒在快凝聚时的分形维数都是在1.86±0.01.当电解质浓度降低,凝聚速率变慢,分形维数增加,最大达到2.01±0.02,但不会形成重力条件下的分形维数接近3的结构体.     

耗散粒子动力学和纳维边界条件在微米纳米流体力学模拟中的应用

耗散粒子动力学是一种粗粒化的计算模拟方法,在微米和纳米流体力学中有着广泛的应用.由于界面在微小体积流体中的重要性,边界条件的选取在微米和纳米流体的研究中起到了关键性的作用.我们简单地介绍了耗散粒子动力学的模拟方法,并以此为基础,介绍了能够实现纳维边界条件的可调滑移长度的边界条件模拟方法.通过条纹状图案修饰的超疏水表面的流体力学行为研究,和高分子链在微米纳米流体器件中的运动研究2个例子,耗散粒子动力学结合纳维边界条件的模拟方法的实用性和可靠性得到了证实.     

剪应力下弱作用势胶体颗粒聚团的特点

探讨了不同剪应力下，具有Ｌｅｎｎａｒｄ－Ｊｏｎｅｓ势的胶体颗粒聚团的结构特性，包括簇团的大小分布，径向分布函数，分形维数和原子配位数。研究表明，在弱作用力下，胶体簇团的分布随剪应力的增加而趋向小簇团一边；径向分布函数曲线随剪应力的增加而降低，胡在近程距离内降低得最多；分形维数随剪应力的增加表现为先增加后减小的趋势，其值随模拟条件的不同而在１．９－２．４之间变动。剪应力“场”对分形维数的大小没有太大     

具有多体效应的胶体聚团的特征

考察了多体效应（用Ｓｔｕｔｔｏｎ－Ｃｈｅｎ势，ＳＣ）对胶体聚团的影响并与双体（ＬＪ）势下的结果作了比较。研究表明，ＳＣ和ＬＪ势下簇团的性质有其相似的一面，如：随着剪应力的增加，系统里颗粒的平均势能增加，而每个簇团的颗粒数减少；在较强的剪应力场里，簇团沿剪应力方向（Ｘ轴）被明显拉长且其主轴偏离Ｘ轴等。但它们间的差异也是明显的，在剪应力下ＳＣ系统内颗粒排列得更合理，从而使得平均位能比ＬＪ系统低约１－３     

Cluster Size Effects of Platinum Oxide as Active Sites in Hydrogen Evolution Reactions

The successful design of photocatalytic hydrogen generation from water relies on a thorough understanding of the role of cocatalyst. The photoreactivity was studied as a function of the cluster size of the oxidized platinum cocatalyst. The maximum turnover frequency is found on the smallest‐sized cocatalyst. This effect can be attributed to the size‐dependent proton adsorption.     

小尺寸金属团簇熔化过程的分子动力学模拟

运用分子动力学方法模拟了小尺寸金属团簇的熔化过程, 原子之间的作用采用嵌入原子法(EAM)模型, 计算了均方根键长涨落δ随温度的变化, 以及升温过程中团簇热容的变化. 包含55、56个原子的面心立方(FCC)结构Au团簇的熔化过程是基本相同的. 而同样结构和数目Cu团簇的熔化过程却呈现出不同的趋势. Cu55、Cu56在模拟过程中都出现了FCC结构到二十面体结构的转变. 但由于表面多出了一个原子, Cu56的热容曲线比Cu55多了一个峰, 体系出现了预熔化现象. 这表明小尺寸团簇的固液转变的过程与团簇的原子类型、几何结构和原子数目密切相关.     

团簇尺寸对奇数和偶数磷团簇离子信号强度差异的影响

磷原子形成的奇数和偶数团簇离子的信号存在明显的强度差异. 当团簇离子尺寸n>25时, 奇数团簇离子的信号强度一般会远远超过其邻近的偶数团簇离子. 为更好地理解团簇尺寸对这一现象的影响, 本文通过真空中激光溅射红磷的方法, 利用质谱对磷团簇离子进行了研究和分析. 结果表明这种方法可以产生较大尺寸(n~500)的磷团簇离子. 进一步对团簇离子的强度分布进行分析表明: 随着正负离子团簇尺寸的增加, 奇/偶数离子强度差异都会逐渐减小. 根据它们的变化趋势, 可以预测: 当n>1000时, 奇/偶数离子强度交替的现象可能会消失. 这一结果正反映出团簇在从原子演变到凝聚态物质过程中的桥梁作用.     

Hydrodynamic screening of ring copolymer solutions

The relaxation frequency of the dynamic correlation function for a diblock cyclic copolymer in solution in the zero average condition is calculated in the presence of hydrodynamic interaction. The latter is introduced through the screened Oseen tensor where the hydrodynamic screening length is used as a parameter to determine the range of screening. Substantial differences with the case of linear homopolymer are found, especially in the low q range where the dynamics are much faster and correspond to nondiffusive processes as usually is the case for copolymer systems. As the screening length decreases the dynamics approach the Rouse behavior and the minimum of the relaxation frequency shifts to lower values. The proportionality constant of the relaxation frequency in the intermediate q range Γ(q) → q³/(k_BTη₀) is also investigated as a function of the screening length. © 1994 John Wiley & Sons, Inc.     

Quantum Size Effects in Semiconductor Photocatalysis

The characteristics of photocatalytic systems based on nanostructural semiconductors, characterized by quantum size effects, are discussed. An analysis is made of the consequences of exciton quantum confinement in the volume that are significant for photocatalysis and, in particular, the increase in the energy of photogenerated charges with decrease in the particle size, the photoinduced polarization processes, and also the simultaneous display of these effects. Possible ways of further increasing the effectiveness of systems based on nanostructural semiconductors are examined. __________ Translated from Teoreticheskaya i Eksperimental'naya Khimiya, Vol. 41, No. 4, pp. 199–218, July–August, 2005.     

若干中性配体对Mo—Fe—S簇合物自兜的影响

通过电子吸收光谱的变化研究了一些含N和含P中性配体对MoS_4~(2-)-nFeCl_2-DMF体系形成立方烷型Mo-Fe-S簇合物的可能影响。     

New Cyclosiloxanolate Cluster Complexes of Transition Metals

New cyclosiloxanolate transition metal cluster complex derivatives were prepared. PhSiO₂K reacted with NiX₂ (X₂ = Cl₂ or acac) to give K₂{[η⁶−(PhSiO₂)₆]₂[μ₃−(OH)]₂Ni₄K₄}, a mixed group 1–group 10 metal complex. PhSiO₂Na reacted with Ni(NH₃)₆I₂ to give Na{[η⁶−(PhSiO₂)₆]₂Ni₆(μ₆−I)} as the first example of “encapsulated” I⁻ ion in siloxanolate complexes. The macrocyclic Na₄{[η¹²−(PhSiO₂)₁₂]Cu₄} complex reacted with η⁶−(1,3,5−C₇H₈)Cr(CO)₃ to give the heterobimetallic adduct Na₄{[η¹²−(PhSiO₂)₁₂]Cu₄}· [Cr(CO)₃]₃ as one of the rare examples of heterobimetallic complexes with different oxidation numbers of the metals. The copper derivative {[η⁶−(PhSiO₂)₆]₂Cu₆(n−BuOH)₅} reacted in MeOH/CHCl₃ (1:6) with Et₄NCN to give the hexanuclear complex {[η⁶−(PhSiO₂)₆]₂Cu₆(η²−C₃H₅N₂O₂)₂}, containing 2-amino-2-oxoetanimidic acid methyl ester monoanion ligands, product of an unexpected C–C coupling reaction. This latter complex was characterized also by X-ray diffraction crystal and molecular structure determination. This paper is dedicated to the 70th birthday of Professor Dr. Gunter Schmid (Essen), pioneer of large cluster chemistry, known to friends as GOLD-Schmid, because of his famous discovery of the Au₅₅ cluster. The Authors are proud to be within his many friends.     

Breakup of Agglomerated Clusters of Cellulosic Fines and CaCO3 Particles Exposed to Hydrodynamic Stress

The capacity of fine particles to remain clustered together after being agglomerated by polyelectrolytes plays an important role in papermaking and in the treatment of wastewater. Tests were carried out with agglomerated suspensions of calcium carbonate and primary cellulosic fines in neutral buffer solution. Agglomeration was induced either by a high-charge cationic polyelectrolyte (a coagulant) or by sequential treatment with a coagulant and a very high-mass anionic acrylamide copolymer (a flocculant). Particle size analysis, based on diffraction of laser light, showed that the coagulated suspensions were susceptible to being redispersed by hydrodynamic shear. By contrast, flocculated suspensions were only partly broken up. In a flocculated mixture of CaCO₃ and cellulosic fines, only the cellulosic fines could be separated from each other. The intensity of shear was more critical than its duration. Conventional shear stress was more effective for the breakup of the polyelectrolyte-induced agglomerates versus extensional flow or intense ultrasonic vibrations.     

The Role of Interface on the Properties of Cluster Assemblies

Atomic clusters characterized by finite size, low dimensionality, and reduced coordination number exhibit many novel properties that are very different from their bulk. As these clusters are assembled, their properties can be significantly altered due to the interaction of these clusters with each other as well as with their support. This paper provides a brief review of the cluster properties that are affected when clusters are deposited on metallic or organic substrates, isolated in matrices or in zeolite cages, coated with acetate ligands, or simply allowed to self-assemble without the presence of any reactive species. It is shown that the interface between the clusters and their support can play an important role on the properties of clusters as their unique characteristics do.     

Size dependent structural and electronic properties of MgO nanotube clusters

MgO nanotube clusters which cross sections are composed of two‐, three‐, four‐, and five‐membered rings are constructed and studied by the density functional theory at B3LYP/6‐31G(d) level. The variations of bond length present anisotropic effect. Three‐membered ring nanotube cluster is the most stable tube among these MgO isomers. Mixed covalent and ionic bonding always exists in MgO nanotube clusters. With increasing length of MgO nanotube clusters, the averaged atomic charge increases, and converge to 1.227; the s‐p separation of O bands decreases; whereas energy gap nearby frontier orbitals present dramatic difference corresponding to various structure family. It is possible that MgO nanotube clusters show electronic properties of semiconductor. An interpretation for MgO nanotube clusters fabricated by simply thermal methods is proposed. The structural and electronic properties of MgO nanotube clusters are discussed systematically in details. © 2008 Wiley Periodicals, Inc. Int J Quantum Chem, 2009