分子聚集溶液理论及其应用

本文应用经典热力学和分子热力学方法建立了分子聚集溶液理论。该理论具有通用性；它不仅适用于非电解质溶液，而且也可应用于电解质溶液。另外，溶液的分子聚集度参数与组分浓度的相关性规律还可用来描述电解质溶液的传递性质。     

Raman scattering,luminescence, and absorption edge under hydrostatic pressures of layered BiI3 and SbI3

Raman scattering from BiI₃ and SbI₃ crystals has been studied at hydrostatic pressures up to 2 GPa. The wavenumbers monotonically increased with pressure for all modes in BiI₃. Although both crystals belong to the same space group, the pressure coefficients of SbI₃ were significantly different from those of BiI₃. At pressure P₀ = 0.92 ± 0.01 GPa, the pressure coefficients of all modes changed. Above P₀, all modes in SbI₃ had positive pressure coefficients as they have in BiI₃. By comparing this unusual behavior of the Raman lines in SbI₃ around P₀ with the results in BiI₃ and comparing the two lattice structures, we suggest that the type of bonding of SbI₃ changes to become more ionic and hence more similar to the bonding of BiI₃. This change in structure is supported by changes in the bandwidth of the self‐trapped exciton (STE) luminescence and the slope of the absorption edge photon energy versus pressure. Copyright © 2007 John Wiley & Sons, Ltd.     

Controlling Surface Interactions with Grafted Polymers

The interactions between surfaces modified with grafted polymers is studied theoretically. The aim of this work is to find polymer surface modifications that will result in localized attractive interactions between the surfaces. The practical motivation of the work is to find means to control the distance between bilayers and solid supports in supported membranes. Two theoretical approaches are used, the analytical treatment of Alexander and a molecular theory. It is found that grafting each end of the polymer to each surface results in an interaction with a well defined minimum. The location of the minima is found to be very close to the thickness of the polymer layer when the chains are grafted to only one of the surfaces. The predictions of the analytical theory are in excellent agreement with the molecular approach in this case. It is found that increasing the surface coverage increases the strength of the interaction. However, increasing the polymer chain length at fixed surface coverage results in a decrease of the free energy cost associated with separating the surfaces from their optimal distance. For the cases in which grafting to both surfaces is not possible, the molecular theory is used to study the effect of functionalizing segments of the chain to achieve an attractive well. It is found that by functionalizing the free end-groups of the polymers with segments attracted to the membrane, the range of the attractive interaction is significantly larger than the thickness of the unperturbed layer. Functionlizing the middle segments of the chains results in a shorter range attraction but of the same strength as in the end-functionalized layers. The optimal polymer modification is found to be such that the functionlized groups are attracted to the bare surface but are not attracted to the grafting surface. The relevance of the results to the design of experimental surface modifiers is discussed.     

Polymer confinement and bacterial gliding motility

Cyanobacteria and myxobacteria use slime secretion for gliding motility over surfaces. The slime is produced by the nozzle-like pores located on the bacteria surface. To understand the mechanism of gliding motion and its relation to slime polymerization, we have performed molecular dynamics simulations of a molecular nozzle with growing inside polymer chains. These simulations show that the compression of polymer chains inside the nozzle is a driving force for propulsion. There is a linear relationship between the average nozzle velocity and the chain polymerization rate with a proportionality coefficient dependent on the geometric characteristics of the nozzle such as its length and friction coefficient. This minimal model of the molecular engine was used to explain the gliding motion of bacteria over surfaces.     

Mach–Zehnder interferometers in photonic crystals

Photonic crystal technology allows the creation of optical waveguides with low sharp-bending losses as well as ultra-low group velocity. This last property is particularly interesting to develop highly-compact optical devices based on the controlled modification of the optical phase of the signals traveling through the waveguides. Among these devices, the Mach–Zehnder interferometer acquires fundamental importance because it can be used as a building block of more complex optical devices and functionalities such as optical filters, wavelength demultiplexers, channels interleavers, intensity modulators, switches and optical gates. In this paper, the performance of a Mach–Zehnder interferometer consisting of two coupled-cavity waveguides with different lengths created in a two-dimensional photonic crystal is theoretically analyzed. We also provide simulation results using a finite-difference time-domain code that confirm the theoretical analysis. The main limitations in the performance of the structure are addressed and discussed.     

Effect of aerosil dispersions on the nematic-to-isotropic interface

The effect of silica aerosils on the kinetics of the first-order nematic-isotropic (NI) phase transition is phenomenologically described in the framework of the time-dependent Landau-Ginzburg equation. A steady-state solution to the equation is presented such that the NI interface may propagate with a solitary-like wave profile under constant quenching. The results provide a plausible basis for the interpretation of the dynamical effects of quenched disorder in the liquid-crystal systems, caused by randomly interconnected porous media, such as aerosils. In the low silica aerosil ρ_s ( ≤0.1 g/cm^3) regime, the calculated values of the interface velocity v(T,ρ_s), the interface thickness κ(T,ρ_s), and the critical radius of a spherical nucleus of new nematic phase in a bulk isotropic environment, composed of polar molecules, such as 4-n-octyl- 4^′- cyanobiphenyl and 4-n-heptyl- 4^′- cyanobiphenyl shows that the effect of silica aerosils on the kinetics is reflected in a shifting of the set of temperature-dependent curves to lower temperature values.-1     

Molecular dynamical study of the energy relaxation processes after heating the vibrational degree of freedom in a diatomic molecular crystal

Energy relaxation processes initiated by sudden heating of the vibrational degree of freedom were studied with molecular dynamical method. A unit cell of bee structure containing 128 diatomic molecules with periodic boundary conditions was considered. Compound Morse potential was assumed as the atom-atom interactions. It was found that the logarithra of the equilibration time depends linearly upon a factorf ₂₁ which is proportional to the frequency ratio of the intra- and inter-molecular vibrations. The project is supported by the National Natural Science Foundation of China.     

从分子结构式估算凝聚炸药最高装药密度

本文应用对应态原理建立了一种从凝聚炸药的分子结构式估算其最高装药密度的经验方法。应用此法对101种环状化合物的密度进行了估算,计算值与实验值的平均偏差为1.08％。与类似工作相比,本文方法精度较高,使用方便。     

飞秒强激光场中水分子的电离激发

本文运用含时密度泛函理论和分子动力学非绝热耦合的方法, 研究了水分子在不同极化方向的激光场中的电离和动力学行为. 计算结果表明, 对应相同的极化方向, 随着激光强度的增加, 水分子的电离增强; 对于相同强度的激光, 当激光极化方向沿水分子对称轴方向时, 水分子的电离最强, 当激光极化方向垂直水分子对称轴方向时, 水分子电离受到最大程度的抑制. 对水分子偶极矩的研究表明, 当分子处于线性响应区域时, x方向的激光只能激发起x方向的偶极振动而y方向的激光只能激发起y方向的偶极振动. 对水分子的键长和键角的研究表明, 在激光场中水分子的键长变长, 键角变大, 但变化幅度随着激光极化角的增大而减小. 此外, 研究还发现, 虽然在不同极化方向的激光脉冲的驱动下, 水分子OH键的振动频率与激光频率相当, 在脉冲关闭后, 振动频率减小, 但激光场的极化方向对水分子振动模式具有选择性. 关键词： 含时密度泛函理论 分子动力学 水分子 电离     

理论研究激光强度对H2+分子高次谐波产生的影响

本文通过求解非波恩-奥本海默近似条件下的一维含时薛定谔方程来研究脉冲强度对H₂⁺分子高次谐波的影响.由于干涉相消,在啁啾激光场的条件下在谐波谱中出现了干涉最小值.我们用全量子方法计算的时频分布图分析了分子高次谐波产生中的微观机制.此外,数值计算结果显示随着脉冲强度的增加电子的有质动力势随之增加,同时干涉最小值的位置移向谐波的高阶部分.