Structured water chains in external electric fields

ABSTRACT

We study the structural, energetic and electronic properties of the structured water chain clusters within the density functional theory. We refer the structured water chains to those water clusters that have specific geometric patterns stretched along one direction. External electric field required to keep the structures open chain, thereby preventing them to form closed structures, is applied along the length of the chain. The structures are essentially periodic with basic repeating unit consisting of the corner- or edge-sharing 4-, 5- or 6-membered ring water clusters. Our calculations underscore the possible existence of such structured water clusters in the electrostatic environments, which we simulate in its simplicity employing a dipolar, uniform and static electric field. Analysis reveals that the 5-membered ring water chain clusters, i.e. the pentamer chain clusters have the lowest average dipole moment per water molecule while the threshold field, that marks the onset of the field-induced closure of the HOMO (highest occupied molecular orbital)-LUMO (lowest unoccupied molecular orbital) energy gap, is highest, followed by that for the tetramer and hexamer chains. The results suggest that the pentamer chains are the most stable clusters over a wide range of electric fields.     

Strong Squeezing of Duffing Oscillator in a Highly Dissipative Optomechanical Cavity System

In the conventional scheme of generating strong mechanical squeezing by the joint effect between mechanical parametric amplification and sideband cooling, the resolved sideband condition is required so as to overcome the quantum backaction heating. In the unresolved sideband regime, to suppress the quantum backaction, a χ⁽²⁾ nonlinear medium is introduced to the cavity. The result shows that the quantum backaction heating effect caused by unwanted counter-rotating term can be completely removed. Hence, the strong mechanical squeezing can be obtained even for the system far from the resolved-sideband regime.     

Optimization of anionic conductivity through the coexistence of ionomer cluster and backbone-backbone morphologies in anion exchange membranes

Random copolymers of poly(4-vinylpyridine) and polyisoprene were synthesized, and subsequently quaternized with 1-alkylbromides. The number of carbons on the pendant side-chain of the resultant comb-shaped polymer, n, ranged from 2–8. The comb-shaped polymers were crosslinked employing thiol-ene chemistry to give mechanically robust ion conducting membranes. Analysis by wide and medium-angle X-ray scattering show three morphology regimes that are dependent on the number of carbons on the pendant side-chains. When n = 2, ionomer cluster morphology was dominant, when n = 8 backbone-backbone morphology was dominant, and when n = 3–6, the membrane showed a coexistence of both ionomer cluster and backbone-backbone morphologies. Evaluation of the water uptake of the membranes showed a maximum water uptake per cation of 9.5 when n = 5 at 95% relative humidity (RH) and 60°C. Conductivity of the samples characterized by electrochemical impedance spectroscopy showed bromide conductivity as high as 110 mS/cm when n = 3 at 95% RH and 90°C.     

消光式核壳二聚体传感器的设计与光谱特性分析

根据ITO/Au纳米核壳二聚体粒子在生物医学领域的应用合理性,设计了一种实时检测生物液体的核壳二聚体探针消光式传感器;由偶极子理论推导出输出波长与外界环境折射率关系;利用MATLAB设计ITO/Au纳米核壳二聚体粒子结构;采用软件DDSCAT7.3结合离散偶极近似法,利用二聚体有效半径模拟计算了300~950nm可见光到红外光波段不同核壳比、二聚体间距、以及不同介质折射率的消光光谱;根据传感芯片折射率与偶极共振、耦合八级共振的响应关系得出ITO/Au二聚体的折射率灵敏特性。与传统Ag/Au核壳纳米粒子相比,ITO/Au纳米核壳二聚体结构引入了可作为传感芯片灵敏性自参考参数的耦合八级共振峰,同时ITO/Au二聚体结构的折射率灵敏度可达到419nm/RIU。这些工作及其结果对制作消光式传感器具有重要的意义。     

Magneto-sensitive smart soft material and magnetorheological mechanism

磁敏智能软材料是一类将微米或纳米尺度的磁性颗粒分散在不同基体中制备而成的多功能复合材料.由于其流变性能在外磁场的调控下可以实现连续、快速、可逆的改变,因此在建筑、振动控制和汽车工业等领域得到了广泛地应用.本文首先介绍了磁敏智能软材料发展历史及分类,分析了不同种类的磁敏智能软材料的特点和存在的科学问题;然后从实验和理论两个方面讨论了磁流变机理的研究现状;最后从实际应用的角度对这类材料未来的发展方向进行了展望.     

Self-Assembly of C3 Symmetric Rigid Macrolactams into Very Polar and Porous Trigonal Crystals

Cyclohexane and cyclotri-β-alanyl have been used as scaffolds for the design of new C₃-symmetric rings incorporating conjugated alkenes and dienes. All three C₃-symmetric lactams share the same triangular shape and their crystal system is trigonal. They all belong to the R3 space group, R3m, R3 and R3c, for the increasingly large 12-, 18- and 24-membered rigid rings, respectively. All lactams stack on top of each other, through H-bonds and van der Waals noncovalent interactions, leading to endless supramolecular cylinders and tubes. The largest member of the family leads to tubes, the central pores of which is wide enough to let water in. A common feature of all the lactams is their very large dipole, of around 9 D, according to DFT calculations. Surprisingly, all the resulting cylinders and tubes pack side by side in the crystals, with all the dipoles pointing to the same direction. As a result, all three crystals are anisotropic and appear to be the first members of a new kind of highly polar crystals.     

飞秒激光场中原子所受光学偶极力研究

通过求解全波矢布洛赫方程研究了两能级原子与飞秒超快激光脉冲的相互作用过程,计算了不同拉比频率取值下原子所受光学偶极力和粒子数布居随时间的演化情况,分析了光场失谐量对光学势分布情况的影响.研究发现:由飞秒激光场产生的横向光力的时间平均值并不等于零,而是随着拉比频率的增加呈现振荡的增大趋势;纵向光力的时间平均作用也并非是拉比频率的单调函数,而是随着拉比频率的增加呈现周期性的振荡分布特性;光学势的分布对光场的失谐量具有明显的依赖性,随着失谐量的变化,光学势的性质也随之发生了改变.     

瞬态荧光方法研究溶剂诱导的三苯胺衍生物的对称性破缺电荷转移动力学

在缺乏特征红外振动的情况下追踪具有四极或八极对称性分子的激发态对称性破缺电荷转移通常是很困难的.本文以一种具有八极对称性的三苯胺衍生物为研究对象,利用飞秒时间分辨瞬态荧光光谱方法获得发光跃迁偶极矩的演化动力学,进而实时表征了其溶剂诱导对称性破缺电荷转移的动力学过程.当该分子处于弱极性甲苯溶液中时,在激发态弛豫过程中其发射偶极矩变化较小;当处于较强极性的四氢呋喃溶液中时,其发射偶极矩在数皮秒内快速减小.在对比单体偶极分子的荧光动力学后,推断八极分子的发光态在强极性溶剂中经历溶剂诱导的结构变化,由激子耦合的八极对称性降低至激发定域的偶极对称性;而在较弱极性的溶剂中,其八极对称性在溶剂化稳定中得以较大程度的保持.     

钫原子磁偶极超精细结构常数及其同位素的磁偶极矩的理论计算

应用基于B样条基组的相对论耦合簇理论方法,计算了~(212)Fr原子的n S (n=7—12), n P (n=7—12)和n D (n=6—11)态的磁偶极超精细结构常数.与精确实验值的比较说明这套理论方法能精确计算出磁偶极超精细结构常数,其中7P态的磁偶极超精细常数的理论值与实验值之间的差异小于1%.在忽略场移效应对Fr原子7P态超精细结构常数的影响下,通过结合实验值进一步定出了~(207-213,220-228)Fr核磁偶极矩μ,这些值与已有的测量值具有非常好的一致性.本文报道了12S, n P (n=9—12)和n D (n=10—11)态的磁偶极超精细结构常数.