界面氢键对受限水结构和动态特性的影响

应用反应力场分子动力学方法, 模拟了水限制在全羟基化二氧化硅晶体表面间的弛豫过程, 研究了基底表面与水形成的界面氢键, 及其对受限水结构和动态特性行为的影响. 当基底表面硅醇固定时, 靠近基底表面水分子中的氧原子与基底表面的氢原子形成强氢键, 这使得靠近表面水分子中的氧原子比对应的氢原子更靠近基底表面, 从而水分子的偶极矩远离表面. 当基底表面硅醇可动时, 靠近基底表面水分子与基底表面原子形成两种强氢键, 一种是水分子中的氧原子与表面的氢原子形成的强氢键, 数量较少, 另一种是水分子中的氢原子与表面的氧原子形成的强氢键, 数量较多, 这使得靠近表面水分子中的氢原子比对应的氧原子更靠近表面, 从而水分子的偶极矩指向表面. 在相同几何间距下, 当基底表面硅醇可动时, 表面的活动性使得几何限制作用减弱, 导致了受限水分层现象没有固定表面限制下的明显. 此外, 固定表面比可动表面与水形成的界面氢键作用较强, 数量较多, 导致了可动表面限制下水的运动更为剧烈.     

醇类抑制剂对甲烷水合物形成的影响

在本工作中,甲烷水合物的生长动力学是通过甲醇、乙醇、乙二醇三种不同醇类抑制剂存在下的分子动力学模拟研究的.模拟结果发现,三种醇类都可作为甲烷水合物的抑制剂,醇类分子中的亲水性羟基极大地破坏了水合物笼的结构,并且羟基可以与局部的液态水分子形成氢键,从而增加了形成水合物笼型结构的难度,导致甲烷水合物的生长速率降低.对于甲醇分子,甲醇分子的亲水性羟基与水分子形成氢键从而破坏了水分子结构,而亲油性甲基对周围的水分子具有簇效应,两者都会降低水合物生长速率;对于乙二醇和乙醇分子,它们只含有羟基,特别是乙二醇分子含有两个羟基,其对H₂O分子有很强的吸附作用,导致水合物生长速率降低.在抑制效果方面,甲醇分子最优,乙二醇稍微优于乙醇.     

利用扫描隧道显微镜研究水分子在Cu(110)表面的吸附与分解

利用扫描隧道显微镜研究水分子在吸附有氧原子的Cu(110)表面的吸附与分解过程.室温条件下,氧原子(O)在Cu(110)表面吸附并自组装形成规则的沿[001]方向的(2×1)Cu-O链状结构.将吸附有氧原子的Cu(110)样品置于77 K低温条件下观察水分子的吸附与分解,发现在低温下水分子通过氢键与Cu-O链中的氧原子键合而吸附于Cu-O链的顶部和周围,吸附于Cu-O链周围的水分子自组装形成规则的六边形网状结构.通过针尖隧穿电子激发,六边形网状结构中的水分子与氧原子发生化学反应,反应生成的羟基与未参与反应的水分子键合在裸露的Cu(110)表面形成蜂窝网状结构.研究结果表明,Cu(110)表面吸附的氧原子有助于水分子在金属表面的吸附和组装,同时可以催化金属表面水分子的分解反应,对水汽转换实验研究具有一定的指导意义.     

基于正六边形多开口的新型双频带左手材料

本文提出了基于正六边形多开口的新型双频带磁谐振体.在微波衬底材料的一面放置交错多开口的两个正六边形金属环,多开口结构破坏了环间耦合电容,从而使两环形成相对独立的两个谐振网络实现双频带效应.最后将该谐振结构的另一面放置金属导线形成一个双频带的新型左手材料.文中利用HFSS软件仿真和等效参数提取的方法,分析和验证该结构的正确性.     

基于三角谐振环的新型六边形谐振环金属线复合周期结构左手材料性质研究

通过实验及仿真研究了三角谐振环组合新型六边形谐振环金属线复合周期结构左手材料.仿真研究了以金属铜三角开口谐振环（SRRs）为基本单元的周期结构负磁导率材料,与闭口环（CSRRs）结果对比发现三角开口谐振环能产生很好的谐振效果即能产生负磁导率,并且多层单元仿真发现多个谐振环耦合能提高谐振频率并加宽谐振频段;设计、制作并实验和仿真研究了三角开口环为基本单元的六边形谐振环金属线复合周期结构左手材料,仿真结果在98GHz附近出现良好负折射效应,实验验证在93—108 GHz出现良好负折射效应,与仿真结果具有良好的一致性.该研究对新型周期结构左手材料的研究、设计和研制具有重要的科学意义和应用前景. 关键词： 左手材料 三角环组成的六边形谐振环 负折射     

用稳态和时间分辨荧光光谱研究乙醇-水分子团簇的可能类型

研究了紫外光照射乙醇－水混合溶液的稳态和时间分辨荧光光谱.通过检测其荧光光谱和激发光谱,得到了稳态发射光谱的三个荧光峰,峰值分别位于290 nm、305 nm、330 nm,相应的最佳激励光分别为265 nm, 280 nm 和236 nm.在荧光光谱峰值波长处分别监测其荧光强度随时间的衰变过程,将获得的荧光衰减动力学曲线采用指数拟合并进行解卷积处理获得不同荧光光子的寿命值.乙醇－水溶液稳态光谱的特点和三个不同的荧光寿命都表明了溶液中含有三个不同的生色团,分析认为乙醇和水分子间通过氢键作用形成了不同结构的团簇分子.     

对浸入水或甲醇中的石墨氧化物的理论研究 (cited: 3)

采用密度泛函理论优化了含水和不含水的石墨氧化物的多种结构. 当层间没有水分子时,优化的层间距在6 ?左右,小于6.5～7 ?的实验值. 反之,水石墨氧化物的层间距和实验值符合很好. 基于优化的石墨氧化物结构,用分子动力学方法模拟了水或甲醇中的石墨氧化物. 对于不含水的石墨氧化物,水和甲醇分子不进入其层间. 而对于含水的石墨氧化物,液体分子进入层间,增大了层间距,半定量地重复了实验现象.     

一种新型混合双包层光子晶体光纤的色散特性研究

以多极法理论为基础,设计了一种混合双包层结构的光子晶体光纤.通过改变其五层空气孔的四个结构参数（内层空气孔直径、外层空气孔直径、六边形孔间距和八边形孔间距）,理论上实现了色散绝对值在144—20 μm的波段内变化仅为125 ps·km^-1·nm^-1的平坦色散特性.在此情况下对其损耗进行了数值模拟,使所设计的光纤在144—20 μm的宽波段范围内具有小于0005 dB/km的低限制损耗特性.     

氩气/空气介质阻挡放电自组织超六边形斑图实验研究

采用双水电极介质阻挡放电装置,在氩气/空气混合气体放电中,在三种边界条件下得到了一种新型的超六边形斑图.给出了超六边形斑图的傅里叶变换及其不同模强度随旋转角的变化.实验测量了超六边形斑图随空气含量和外加电压变化的相图.研究了超六边形斑图的时空动力学,发现超六边形斑图是由两套子结构嵌套而成.在四边形边界条件下,研究了放电面积的大小对斑图模式选择的影响.发现超四边形斑图的形成受边界条件影响很大,而超六边形斑图则是自组织的结果. 关键词： 介质阻挡放电 超六边形斑图 时空动力学 边界条件     

二维衰减全反射红外光谱研究水在聚酰亚胺/二氧化硅纳米高分子复合膜中的吸附扩散行为

考虑到基于聚酰亚胺衍生物的电子器件的稳定性和性能,运用二维衰减全反射红外相关光潜研究了水在聚酰亚胺衍生物:poly(4’4- oxydiphenylene pyromellitimide)和二氧化硅的纳米高分子复合膜中的动态吸附和扩散行为．二维相关光谱区分出了三种不同氢键强度的水分子状态,同时,氢键的数量和强度还对不同状态水分子的扩散速率起了决定性的作用,和PI聚合物本身以及PI表面残留的硅酸形成氢键的水分子的扩散速度则最慢.     

Surface-induced ordering of a molecular fluid of flat hexagonal structure in a narrow graphite slit

We systematically investigate by Monte Carlo simulations the role of the wall structure on a fluid of flat hexagonal molecules confined between two graphite walls. Our simulations show that the centers of mass of the molecules in different layers undergo an order-disorder transition as the wall separation increases, irrespective of the details of the wall structure. The wall structure thus becomes insignificant for the intervening fluid even down to a surprisingly low wall separation.     

Nature of the transition from two- to three-dimensional ordering in a confined colloidal suspension

We report the results of extensive molecular dynamics simulations of solid-to-solid transitions in two- to six-layer colloidal suspensions confined between two smooth parallel walls. The studies are designed to elucidate the ordered particle packings that interpolate between the structures of two- and three-dimensional crystals in a confined space. At a fixed density per layer, as the wall separation increases we find a sequence of stable phases, each characterized by uniform amplitude buckling along the normal to the layer planes. The buckling is coupled to an in-plane ordering transition. The buckled phases alternate with phases whose structures contain only parallel planes of particles. The relative densities of the positively and negatively displaced particles in a buckled layer, the in-plane structures, and the behavior with respect to increasing wall separation of the split density distribution that characterizes a buckled layer, clearly identify these layers as intermediates in the reconstructive transformations ntriangle up-->(n+1) square that occur when the character of the constrained space evolves from being two dimensional to being three dimensional (triangle up denotes layers with hexagonal packing symmetry, while square denotes layers with square packing symmetry). The two transitions, ntriangle up-->n-buckled-->(n+1) square, are found to be first order.     

Thermoluminescence study of the amorphisation of hexagonal ice by irradiation at 77 K

This paper reports on a thermoluminescence study of D₂O ice I_h. A sample of hexagonal (I_h) ice is irradiated by a 100 MeV X-ray source at 77 K. The emission spectrum that is measured immediately after the end of the irradiation process has the thermoluminescent behaviour of amorphous ice. The kinetic transition is followed to the stable form, taking place at 85 K. The relaxation time of the transition is of the order of 5 minutes. It is concluded that, due to irradiation, a few outer layers of ice I_h are converted to the low-density amorphous form of ice, which then converts to cubic ice. Although complex to quantify, thermoluminescence appears to be, in the present study, particularly sensitive to the time evolution of irradiated samples.     

石墨狭缝中甲烷吸附的分子动力学模拟

用分子动力学模拟研究石墨狭缝中甲烷的吸附,考察狭缝宽度和温度对甲烷吸附的影响.模拟发现甲烷在石墨狭缝中出现分层现象,吸附层中甲烷具有类液特征,第一吸附层内甲烷中总有两个氢原子的连线与另外两个氢原子的连线分别位于平行于狭缝壁的两个平面内,游离层中甲烷呈现气体的特征;碳原子间的平均作用势说明吸附层中甲烷分子间结合能力大于游离层,吸附态是甲烷在石墨狭缝中的主要赋存形式之一;伦敦力以及由吸附层净电荷产生的电场力是甲烷吸附和分层的主要原因;甲烷的吸附量随狭缝宽度增大或温度升高而减少,当狭缝宽度小于16.46Å时,甲烷仅以吸附形态存在.甲烷在第一吸附层中的扩散能力最弱、游离层中最强,甲烷扩散系数随狭缝宽度的增大或温度的升高而增大.     

Effective optical constants and effective optical properties of ultrathin trilayer structures

This work presents an extension of the characteristic effective medium approximation (CEMA) to ultrathin trilayer systems. The extension has been carried out analytically and is supported by corresponding calculations of the effective optical constants of Cu-Au-Cu and Ag-SiO-Ag trilayer systems using the CEMA approximation. This work is in essence a generalization of the characteristic effective medium approximation introduced earlier for ultrathin bilayer structures. This method is used to derive the effective optical constants of a trilayer system, consisting of three thin layers with each constituent layer of thickness much less than the wavelength of the incident radiation. Within this regime a trilayer system is viewed as one effective layer referred to as an effective stack (ES) with well defined effective optical constants, which can be used to calculate the optical properties of the trilayer stack within a specified wavelength range. The CEMA based calculations of the effective optical constants are applied to two trilayer systems with a total of five stacks. Three are Cu-Au-Cu and two are Ag-SiO-Ag stacks. The thicknesses of the parent layers in the Cu-Au-Cu stack range from 3 to 30 nm for Cu and 4 to 40 nm for Au; in the Ag-SiO-Ag stack the constituent layers are 6 nm for Ag, but range from 5 to 10 nm for SiO. This study is for normal or near normal incidence spectroscopy in a wavelength range that extends from visible to near infrared. The agreement between CEMA based ES stack results and those of the standard CMT technique is very satisfactory.     

Freezing and melting of binary mixtures confined in a nanopore

This paper reports on a Grand Canonical Monte Carlo study of the freezing and melting of Lennard–Jones Ar/Kr mixtures confined in a slit pore composed of two strongly attractive structureless walls. For all molar compositions and temperatures, the pore, which has a width of 1.44?nm, accommodates two contact layers and one inner layer. Different wall/fluid interactions are considered, corresponding to pore walls that have a larger affinity for either Ar or Kr. The solid/liquid phase diagram of the confined mixture is determined and results compared with data for the bulk mixture. The structure of the confined mixture is studied using 2D order parameters and both positional g(r) and bond orientational G₆(r) pair correlation functions. It is found that in the confined solid phase, both the contact and inner layers have a hexagonal crystal structure. It is shown that the freezing temperature of the Ar/Kr confined mixture is higher than the bulk freezing point for all molar compositions. Also, it is found that the freezing temperature becomes larger as the ratio α of the wall/fluid to the fluid/fluid interactions increases, in agreement with previous simulation studies on pure substances confined in nanopores. In the case of pore walls having a stronger affinity for Kr atoms (ε _Ar/W<ε _Kr/W), it is observed that both the contact and inner layers of the confined mixture undergo, at the same temperature, a transition from the liquid phase to the crystal phase. The freezing of Ar/Kr mixtures confined between the walls having a stronger affinity for Ar (ε _Ar/W?>?ε _Kr/W) is more complex: for Kr molar concentration lower than 0.35, we observe the presence of an intermediate state between all layers being 2D hexagonal crystals and all the layers being liquid. This intermediate state consists of a crystalline contact layer and a liquid-like inner layer. It is also shown that the qualitative variations of the increase of freezing temperature with the molar composition depend on the affinity of the pore wall for the different components. These results confirm that, in addition to the parameter α the ratio of the wall/fluid interactions for the two species, η=?_Ar/W/?_Kr/W, is a key variable in determining the freezing and melting behaviour of the confined mixture.     

Dislocation mechanism for transformation between cubic ice Ic and hexagonal ice Ih

Cubic ice I_c is metastable, yet can form by the freezing of supercooled water, vapour deposition at low temperatures and by depressurizing high-pressure forms of ice. Its structure differs from that of common hexagonal ice I_h in the order its molecular layers are stacked. This stacking order, however, typically has considerable disorder; that is, not purely cubic, but alternating in hexagonal and cubic layers. In time, stacking-disordered ice gradually decreases in cubicity (fraction having cubic structure), transforming to hexagonal ice. But, how does this disorder originate and how does it transform to hexagonal ice? Here we use numerical data on dislocations in hexagonal ice I_h to show that (1) stacking-disordered ice (or I_c) can be viewed as fine-grained polycrystalline ice with a high density of extended dislocations, each a widely extended stacking fault bounded by partial dislocations, and (2) the transformation from ice I_c to I_h is caused by the reaction and motion of these partial dislocations. Moreover, the stacking disorder may be in either a higher stored energy state consisting of a sub-boundary network arrangement of partial dislocations bounding stacking faults, or a lower stored energy state consisting of a grain structure with a high density of stacking faults, but without bounding partial dislocations. Each state transforms to I_h differently, with a duration to fully transform that strongly depends on temperature and crystal grain size. The results are consistent with the observed transformation rates, transformation temperatures and wide range in heat of transformation.     

Hydromagnetic elastico-viscous fluid flow between two parallel walls: Velocity field.-I

Summary The effect of the elastic properties of the fluid on the MHD Couette flow of a conducting viscous fluid between two parallel walls is studied when one wall is fixed and the other is moving periodically in time. Exact solution for the velocity field in the boundary layer is obtained. Also expressions for the shear stress at different layers and the skin-friction at the two walls have been obtained.     

New Two-Dimensional Ice Models

This paper presents a new approach for enumerating all hydrogen bond arrangements of ice-like systems with periodic boundary conditions. It is founded on a topological procedure for the dimensional reduction and a new variant of the transfer matrix method based on small conditional transfer matrices. We consider a couple of new two-dimensional ice models on very unusual lattices. One of them is the twisted square ice model with crossing H-bonds. The other is the digonal-hexagonal model with double H-bonds. In spite of their uncommonness, these models are quite realistic, because from the standpoint of combinatorics and topology they are equivalent to the layers of usual hexagonal ice Ih under periodic boundary conditions in one of the directions. The exact proton configuration statistics for a number of 2D-expanded unit cells of hexagonal ice Ih and the residual entropy of the new ice models in the large system limit are presented.     

Spin-dependent scattering in multilayered magnetic rings

Narrow mesoscopic NiFe/Cu/Co elliptical rings exhibit room-temperature giant magnetoresistance with distinct resistance levels corresponding to three different micromagnetic states. The highest and lowest resistance states of the multilayer rings correspond to the Co layer being in a bidomain state, antiparallel or parallel, respectively, to the NiFe, while the intermediate resistance corresponds to the Co layer being in a vortex state. Micromagnetic simulations suggest that the behavior of these rings is dominated by magnetostatic interactions between the domain walls in the Co and NiFe layers. Additional magnetization states in the NiFe at low applied fields can account for the minor loop behavior.