1,8-二巯基芘分子电学特性的理论研究

在第一性原理的基础上 ,对 1,8 二巯基芘分子的电学特性进行了理论研究 .采用了 3个Au原子构成的团簇来模拟Au表面 .首先利用密度泛函理论计算了 1,8 二巯基芘分子的电子结构及其和Au表面的相互作用 ,再利用前线轨道理论和微扰理论定量地确定了该分子和Au表面的相互作用能常数 .最后利用弹性散射格林函数法研究了该分子结的伏 安特性 .计算结果表明 ,分子中的硫原子和Au原子形成很强的共价键 .当外加偏压小于 1V时分子结存在电流禁区 ,随着偏压升高 ,分子结的电导出现平台结构 .分子结的电导特性和其电子结构密切相关 ,扩展分子轨道为电荷的迁移提供了通道 ,而局域轨道对电流贡献很小     

Selfconsistent Electron Energy Distribution Functions in Non Equilibrium oxygen: Effects on the Dissociation Rate

Electron energy distribution functions (edf) in non equilibrium oxygen have been calculated by solving the Boltzmann equation coupled to a system of vibrational master equations. The results show the importance of both superelastic vibrational collisions and of the presence of oxygen atoms in affecting edf. The coupling between the Boltzmann equation and the system of vibrational master equations brings to a temporal evolution of edf, which progressively changes from a cold molecular gas situation (all molecules in the ground vibrational level) to a vibrationally excited molecular gas and finally to a gas composed by oxygen molecules and oxygen atoms. All electronic rate coefficients follow a temporal evolution. due to the corresponding evolution of edf. Finally the present results are used for discussing the dissociation rate of molecular oxygen in electrical discharges.     

Gain and power characteristics of an electron-beam controlled discharge TEA CO2-laser

Gain coefficients and power characteristics of an electron-beam controlled discharge TEA CO₂-laser have been investigated based on computer simulations of the gain kinetic molecular processes in the pumped medium and experimental measurements of the electrical and laser properties of the system. Optimal operation conditions are discussed.     

Electrical properties of unusual ionic melts

The paper reviews the advances that have been made in recent years in the understanding of electrical transport in fully ionized molten salts, partly dissociated molecular liquids and liquid ionic stoichiometric alloys like CsAu. Special emphasis is placed on the recently observed temperature and pressure induced gradual transition between the limiting cases of molecular insulators and ionic melts. At supercritical temperatures salts undergo a continuous transition from an insulating vapour to a highly conducting ionic fluid if the density is increased sufficiently. This transition is due to a shift of the ionization equilibrium between molecules and ions, in favour of the ions, with increasing density. Poorly conducting molten salts and polar substances like water and ammonia also become more ionic, and consequently better conductors, at very high pressures.

Recent thermodynamic, magnetic and electrical measurements on liquid alloys which are composed of two metallic elements and which are non-metallic at definite stoichiometric compositions are discussed. Special emphasis is placed on the liquid Cs-Au system which resembles in many respects the molten alkalimetal halides.     

哈龙1211分子在外电场中的物理特性研究

采用密度泛函理论,在B3LYP/6-311++G(d,p)基组水平上对分子进行优化,研究了在不同外电场下,哈龙1211分子的键长、体系总能量、偶极矩、能级、能隙、电荷分布和红外光谱的变化规律.计算结果表明,电场方向不同,键长的变化趋势也不同.随着外电场(-0.02 a.u.-0.03 a.u.)的增加,C-Br间的键长随x轴方向电场的增加可能先趋于断裂,而C-Cl间的键长随y轴方向电场的增加可能最先趋于断裂,这对利用外电场解离哈龙1211分子有着重要意义.体系总能量和能隙随着外电场的增加先增大后减小,而偶极矩的变化趋势相反.另外,随着电场的增加,红外光谱的最强峰先发生蓝移再发生红移.     

Electrical Conductivity in Polyazomethines: A Novel Mechanism Derived from All Valence MO Calculation and IR Study of Polymer–Dopant Interaction

A simple mechanism is proposed to explain the variation of electrical conductivity in polyazomethines. The results of semiempirical, all valence, molecular orbital calculations obtained from the PM3 method have been employed to arrive at the mechanism. The difference of energy (ΔE) between highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) alone could not explain the variation in electrical conductivity; however, ΔE together with the LUMO electron density at the atoms that lie on the continuous chain could account for the electrical conductivity in these polymers. The LUMO electron density on these centers may be visualized as the carrier movement. In certain polymers there are intrinsic holes in HOMO. The movement of these intrinsic holes also adds to the electrical conduction. The polyazomethines are prepared by the condensation of diamines with azo bis-aldehydes. A few of these polymers were doped with silver nanoparticles. Many of the doped polymers showed substantial enhancement in conductivity. Strong polymer–dopant interaction, identified by IR spectroscopy, is proposed to be responsible for the increase in conductivity.     

哈龙1211分子在外电场中的物理特性研究

采用密度泛函理论,在B3LYP/6-311++G(d,p)基组水平上对分子进行优化,研究了在不同外电场下,哈龙1211分子的键长、体系总能量、偶极矩、能级、能隙、电荷分布和红外光谱的变化规律。计算结果表明,电场方向不同,键长的变化趋势也不同。随着外电场(-0.02a.u.—0.03a.u.)的增加,C-Br间的键长随x轴方向电场的增加可能先趋于断裂,而C-Cl间的键长随y轴方向的增加可能最先趋于断裂,这对利用外电场解离哈龙1211分子有着重要意义。体系总能量和能隙随着外电场的增加先增大后减小,而偶极矩的变化趋势相反。另外,随着电场的增加,红外光谱的最强峰先发生蓝移再发生红移。     

新型航天器电气综合一体化架构研究

随着电子技术的发展,电子元器件的体积越来越小,处理器的运算能力越来越强,存储器的容量越来越大,总线的传输速率越来越高,电子设备的集成度越来越高,成本越来越低。在这样的背景下,航天器电气综合系统设计理念也在与时俱进,为降低电气系统体积重量和功耗,以提高航天器的任务能力,同时为加快研制进度,降低研制成本,迫切需要开展新型航天器电气综合一体化架构研究,这篇文章主要对比国外航空航天领域飞行器先进电气综合系统架构,分析了目前国内航天器电气系统综合设计中存在的缺陷和弊端,结合我国未来新型航天器对电气综合系统的需求,提出了我国新一代航天器电气综合系统一体化设计的基本原则,并对系统软硬件体系架构及具体的功能实现方式进行了初步的设想。     

复杂航天器电气系统潜通路分析技术研究

针对复杂航天器电气系统功能接口复杂、信号类型众多的特点,系统分析了导致潜通路存在的接口冗余、时序逻辑复杂、接地类型多等客观原因。明确了复杂航天器电气系统潜通路分析工作流程,并简要论述了潜通路分析的准备工作中的单机电气接口数据收集、电路原理图设计与简化的方法和要点,结合潜通路仿真建模分析及优化方法,总结了复杂航天器电气系统潜通路故障定位的潜在路径搜索与分析、识别与验证的步骤。提出了复杂航天器电气系统预防潜通路的电气接口信号类型简单化、电气接口隔离、信号流向单一化、接地设计提前规划四项设计原则,并针对某航天器匹配测试阶段发现的潜通路问题的原因及改进措施进行了分析。     

Spezifische Molekültemperaturen in Lichtbögen

By means of thermodynamic equilibrium calculations emission coefficients of molecular bands of A1O and CN are computed. For given pressure and particle concentrations the coefficients show well defined maxima at certain temperatures, usually referred to as normalized temperature of the band system. This behaviour applied to electrical arcs explains the existence of aureoles caused by molecular emission of CN and some metallic oxide bands localized at fixed distances from the centre of the arc. The local temperature of the area of maximum intensity depends not only on the dissociation energy and excitation energy of the molecule in question, but may be altered by the presence of additional components and stoichiometric conditions. Thus, the normalized temperature of band systems arising from heteronuclear molecules cannot be considered as an unchangeable quantity.     

Reversible, nanometer-scale conductance transitions in an organic complex

Reversible conductance transitions are demonstrated on the molecular scale in a complex of 3-nitrobenzal malononitrile and 1, 4-phenylenediamine, by application of local electric field pulses. Both macroscopic and local current-voltage (I/V) measurements show similar electrical bistability behavior. The mechanism of the electrical bistability is discussed.     

分子结电学特性的理论研究

在第一性原理的基础上，对共扼分子2-氨基-5-硝基-1，4-二乙炔基-4’，-苯硫醇基苯(2-amino-5-nitro-1,4-diethyny-4’-benzenethiol-benzene)与金表面形成的分子结的电学特性进行了理论研究.利用密度泛函理论计算了该分子及扩展分子的电子结构；讨论了分子与金表面的相互作用，定量地确定了耦合常数，求出了电子的迁移强度；利用弹性散射格林函数法研究了该分子结的伏—安特性.计算结果表明，当外加偏压小于0.9V时分子结存在电流禁区，随着偏压升高，分子结的电导出现平台特 关键词： 化学吸附 分子结 分子电子学     

Determination of the rotation-diffusion tensor orientation from NMR 13C-1H cross-relaxation rates

Taking advantage of the fact that α,α,2,6 tetrachlorotoluene possesses only one symmetry element (the aromatic ring plane), it proved possible to measure seven different ¹³C-¹H cross-relaxation rates which enable one to determine the three rotation-diffusion coefficients (D_xx , D_yy , D_zz ), in addition to the orientation of the relevant principal axis system (PAS) with respect to a chosen molecular axis system. It turns out that molecular reorientation is strongly anisotropic and that the rotation-diffusion PAS cannot be directly correlated with electrical molecular properties.     

Size effect on organic optoelectronics devices: Example of photovoltaic cell efficiency

Electromagnetic study of organic photovoltaic cells design shows that electrical parameters depend drastically on the active area geometry: we theoretically show that electrical parameters are altered when the cell length becomes greater than one centimeter. Experimental verification is provided with simple molecular heterojunction cells with areas from 0.03 to 0.78 cm².     

Exact analytical results on electronic transport of conjugated polymer junctions: Renormalization method

We study the electrical coherent transport in a typical conjugated polymer connected to molecular electrodes. We provide an exact analytical method to reduce such a system to a uniform wire by employing Green’s function theory and the tight-binding Hamiltonian. The formalism is useful to investigate transport properties of periodic quasi-one dimensional molecular nanowires and polymers in the presence or absence of defects. Some illustrative examples including polyacetylene and poly(p-phenylene) polymers are given to show the ability of our approach. For ideal infinite polyacetylene and poly(p-phenylene) polymers due to dimerization respectively, one and two gaps will appear in the density of states spectra.     

InAs/GaAs (1 1 1)A heteroepitaxial systems

We studied the structural, electrical, and mechanical properties of an InAs thin film grown on GaAs (1 1 1)A substrates by molecular beam epitaxy. In contrast to conventionally used (0 0 1) surfaces, where Stranski–Krastanov growth dominates the highly mismatched heteroepitaxy, layer-by-layer growth of InAs can be established. One of the largest advantages of this unique heteroepitaxial system is that it provides a two-dimensional electron gas system in the near-surface region without the problem of electron depletion. We review the fundamental properties and applications of this unique heteroepitaxial system.     

Self-Assembled CNT-Polymer Hybrids in Single-Walled Carbon Nanotubes Dispersed Aqueous Triblock Copolymer Solutions

We have carried out scanning electron microscopy (SEM), differential scanning calorimetry (DSC), small angle X-ray scattering (SAXS), electrical conductivity, and ¹H NMR studies as a function of temperature on single-walled carbon nanotubes (SWCNTs) dispersed aqueous triblock copolymer (P123) solutions. The single-walled carbon nanotubes in this system aggregate to form bundles, and the bundles aggregate to form net-like structures. Depending on the temperature and phases of the polymer, this system exhibits three different self-assembled CNT-polymer hybrids. We find CNT-unimer hybrid at low temperatures, CNT-micelle hybrid at intermediate temperatures wherein the polymer micelles are adsorbed in the pores of the CNT nets, and another type of CNT-micelle hybrid at high temperatures wherein the polymer micelles are adsorbed on the surface of the CNT bundles. Our DSC thermogram showed two peaks related to these structural changes in the CNT-polymer hybrids. Temperature dependence of the ¹H NMR chemical shifts of the molecular groups of the polymer and the AC electrical conductivity of the composite also showed discontinuous changes at the temperatures at which the CNT-polymer hybrid’s structural changes are seen. Interestingly, for a higher CNT concentration (0.5 wt.%) in the system, the aggregated polymer micelles adsorbed on the CNTs exhibit cone-like and cube-like morphologies at the intermediate and at high temperatures respectively.     

A study on the electrical conduction in solid mixtures of PMMA and a molecular material

DC electrical conduction property of polymer poly(methyl methacrylate) (as host) mixed with a polymeric oxalate-based molecular material (as guest) in different weight percentages has been examined as a function of temperature and applied bias voltage to explore the effect of the guest on the electrical conduction properties of the host. The observed results showed that the room temperature conductivity of the solid mixtures decreases with increasing guest content along with an increase in activation energy. These mixtures are found to be the non-extrinsic type of semiconductors with exponential type of trap distribution. The activation energy and the pre-exponential factor values estimated following Arrhenius relation satisfied the compensation law for electrical conduction. Interestingly, the electrical conduction properties of the solid physical mixture are found to be identical with the melt-mixed analogue though they have morphological differences.     

聚乙烯/银纳米颗粒复合物的分子动力学模拟研究

通过分子动力学模拟对聚乙烯/银纳米颗粒复合物的结构、极化率和红外光谱、热力学性质、力学特性进行计算, 分析其随模拟温度和银颗粒尺寸的变化规律. 模拟结果表明: 聚乙烯/银纳米颗粒复合物为各向同性的无定形结构, 温度升高可提高银纳米颗粒的分散均匀性; 银纳米颗粒表面多个原子层呈现无定形状态, 并在银颗粒和聚乙烯基体的界面形成电极化层, 界面区域随颗粒尺寸和温度的增加分别减小和增加; 与聚乙烯体系相比, 聚乙烯/银纳米颗粒复合物的极化率高很多, 且随温度的升高和银颗粒尺寸的减小而增大; 银颗粒尺寸直接影响界面电偶极矩的强度和振动频率, 红外光谱峰强度和峰位随颗粒尺寸发生变化; 聚乙烯/银纳米颗粒复合物具有比聚乙烯体系更高的等容热容和与聚乙烯体系相反的负值热压力系数, 热容随颗粒尺寸的变化较小, 但随温度的升高而明显减小, 具有显著的温度效应; 热压力系数随温度的变化较小, 但随颗粒尺寸的增加而减小, 具有明显的尺度效应, 温度稳定性更好; 聚乙烯/银纳米颗粒复合物的力学特性表现出各向同性材料的弹性常数张量, 具有比聚乙烯体系更高的杨氏模量和泊松比, 并且都随温度的升高和银颗粒尺寸的增大而减小, 加入银纳米颗粒可有效改善聚乙烯的力学性质. 关键词： 分子动力学模拟 聚合物纳米复合物 纳米颗粒     

Vibration induced memory effects and switching in ac-driven molecular nanojunctions

We investigate bistability and memory effects in a molecular junction weakly coupled to metallic leads with the latter being subject to an adiabatic periodic change of the bias voltage. The system is described by a simple Anderson-Holstein model and its dynamics is calculated via a master equation approach. The controlled electrical switching between the many-body states of the system is achieved due to polaron shift and Franck-Condon blockade in the presence of strong electron-vibron interaction. Particular emphasis is given to the role played by the excited vibronic states in the bistability and hysteretic switching dynamics as a function of the voltage sweeping rates. In general, both the occupation probabilities of the vibronic states and the associated vibron energy show hysteretic behaviour for driving frequencies in a range set by the minimum and maximum lifetimes of the system. The consequences on the transport properties for various driving frequencies and in the limit of DC-bias are also investigated.