Crystal Structure,Electrochemical Properties and Third-order Nonlinear Optical Response of 4-Methyloxy benzaldehyde Thiosemicarbazone and Its Copper(Ⅱ)Complex

Thecurrentsurgeofinterestinthefield0fnon-linearoptics(NL0)isderivedbothfromaquestforafundamentalunderstanding0fthenon-linearprocess,anditSimPortanceinthetechn0logyofphotonics.Amongnon-linearphen0mena,thethird-ordernon-linearophcsoccuPyanimPortantp0sihonbecauseitprovidesthemechanicsforophcalswitching,ophcallogic,andreal-hmeholograPhy"'.0rganicmaterialwithextendednconjugahonsandlargeRdelocalizahonsarewellknownastheimPortantmaterialsofachievinglargethird-ordernonlinearihes3.ForexamPle,thiosen…     

高硅沸石骨架结构及其稳定性的模拟计算(I)*

The lattice energy of a series of high-silica zeolites was determined using the lattice energy minimization method. The results were compared to the lattice energy of dense polymorphs of SiO2. All high-silica zeolites frameworks are only 30～67kJ•mol-1 less stable than α-quartz This may imply that there is little energy barrier to the formation of high-silica zeolites frame-works and explain the structural diversity observed for high-silica zeolites. The relationships of calculated lattice energies and framework Structures was disscussed. The results revealed a good linear relationship between framework density of these molecular sieves and all-silica framework lattice energies.     

An algebraic method that includes Gibbs minimization for performing phase equilibrium calculations for any number of components or phases

The most widely used technique for performing phase equilibria calculations is the K-value method (equality of chemical potentials). This paper proposes a more efficient algorithm to achieve the results that includes Gibbs minimization when we know the number of phases. Using the orthogonal derivatives, the tangent plane equation and mass balances, it is possible to reduce the Gibbs minimization procedure to the task of finding the solution of a system of non-linear equations. Such an operation is easier and faster than finding tangents or areas, and appears to converge as fast as the K-value method. Examples illustrate application of the new technique to two and three phases in equilibrium for binary and ternary mixtures.     

含非线性光学单元侧链液晶共聚物的合成及极化膜的紫外研究

通过自由基共聚合合成了含有高二阶非线性光学活性偶氮单元的侧链液晶共聚物。共聚物的液晶转变温度为ＤＳＣ测定，实验证明当偶氮单元含量超过４０ｍｏｌ％时，共聚物的液晶性消失。通过高压电场对该聚合物膜进行针尖电晕极化取向，并由紫外测试给出了聚合物膜的取向参数及其稳定性，对液晶聚合物的非线性光学性质进行了初步的研究。     

A molecular theory of inhomogeneous broadening,including the correlation between different transitions,in liquids and glasses

Summary We present a molecular theory of the energy distributions for the internal quantum states of a solute in a liquid or glassy solvent. We show that the energy distributions for different states are correlated in a way that depends on the solute-solvent interactions. We show how the theory can be modified easily to describe the transition-energy distributions for different pairs of states, which are of course related to inhomogeneously broadened absorption spectra. We also show that the distributions for different transitions are correlated, and describe how this correlation is measured by nonresonant fluorescence- and phosphorescence-line-narrowing and hole-burning experiments. The theory provides a microscopic framework within which to interpret different phenomenological models. For the case of a Lennard-Jones solute in a Lennard-Jones liquid solvent, we compare our theory to Monte Carlo simulation.     

Spectroelectrochemical and Voltammetric Studies of L‐DOPA

The electrooxidation of L -dopa at GC electrode was studied by in situ UV-vis spectroelectrochemistry (SEC) and cyclic voltammetry. The mechanism of electrooxidation and some reaction parameters were obtained. The results showed that the whole electrooxidation reaction of L -dopa at glassy carbon (GC) electrode was an irreversible electrochemical process followed by a chemical reaction in neutral solution (EC mechanism). The spectroelectrochemical data were treated by the double logarithm method together with nonlinear regression, from which the formal potential E⁰=228 mV, the apparent electron-transfer number of the electrooxidation reaction αn=0.376 (R=0.99, SD=0.26), the standard electrochemical rate constant k⁰=(3.93±0.12)×10⁻4 cm s⁻¹ (SD=1.02×10⁻²), and the formation equilibrium constant of the following chemical reaction k_c=(5.38±0.34)×10⁻¹ s⁻¹ (SD=1.02×10⁻²) were also obtained.     

On the use of local basis sets for localized molecular orbitals

Two procedures are discussed for the direct variational optimization of localized molecular orbitals which are expanded in local subsets of the molecular basis set. It is shown that a Newton-Raphson approach is more efficient than an iterative diagonalization scheme. The effect of the basis-set truncation on the quality ofab-initio SCF results is investigated for Be, Li₂, HF, H₂O, NH₃, CH₄ and C₂H₆.     

Synthesis and nonlinear optical properties of new symmetrically substituted stilbenes

Three new chromophores and trans-4-(N-(ethyl 4″-nitrobenzoate)-N-ethyl amino)-4′-(dimethyl amino) stilbene (DMANHAS) have been synthesized and whose chemical structures have been characterized by ¹H NMR, IR, and elemental analyses. Linear absorption, single-photon-induced fluorescence and two-photon-induced fluorescence are experimentally studied. Trans-4-(N-2-hydroxyethyl-N-ethyl amino)-4′-(dimethyl amino)stilbene (DMAHAS) and trans-4-(N-2-hydroxyethyl-N-ethyl amino)-4′-(diethyl amino)stilbene (DEAHAS) have effective two-photon absorption cross-sections of σ₂=0.91×10⁻⁴⁶ cm⁴ s/photon and σ₂=1.19×10⁻⁴⁶ cm⁴ s/photon at 532 nm by using an open aperture Z-scan technique, respectively. When pumped with 800 nm laser irradiation, DMAHAS and DEAHAS indicate strong two-photon-induced blue fluorescence of 436 and 440 nm, respectively, while trans-4-(N-(ethyl 4″-nitrobenzoate)-N-ethyl amino)-4′-(diethyl amino) stilbene (DEANHAS) and DMANHAS exhibit no fluorescence.     

剪切作用下纳米粘土对LDPE熔体粘弹响应的影响

以LDPE/EVA/纳米粘土复合体系为研究模型,考察了剪切作用下,分散良好的纳米粘土对聚合物基体熔体稳态及瞬态粘弹响应的影响.发现剪切作用下,纳米粘土增加了聚合物熔体粘弹特性对剪切速率、剪切应变及剪切作用史的依赖性,改变了相应的依赖关系.稳态剪切时,纳米粘土的加入使体系第一法向应力差(N1)在低剪切速率区变为负值,而在高剪切速率区N1与粘土的含量无关;同时就瞬态剪切应力及N1的应变依赖关系而言,复合体系明显不同于聚合物基体;预剪切对聚合物基体瞬态粘弹响应几乎没有影响,而当纳米粘土的加入量大于3wt%后,与未经预剪切的样品相比较,经预剪切的复合体系的瞬态剪切应力值、应力过冲程度以及稳态剪切应力值均明显下降,且预剪切前后复合体系达到稳态时其瞬态剪切应力差值随纳米粘土含量的增高而线性增加.此外,纳米粘土的添加对聚合物熔体受剪切作用的非线性粘弹响应存在影响.复合体系熔体呈现特异非线性粘弹响应,其缘由被认为是由于纳米粘土在聚合物基体中剥离分散,或聚合物分子链插层于粘土片层间,形成局部有序结构,受剪切作用而排列取向.     

The Influence of Intermolecular Interactions on Second-Order Susceptibilities of Molecular Crystals: Application to the m-Nitroaniline Crystal

The effects of intermolecular interactions on the second-order susceptibilities (⁽²⁾) of molecular crystals are studied by using a semiempirical quantum–chemical method. These effects are discussed on the basis of the super-molecular approach. The influence of the electrostatic interactions between adjacent unit cells on the tensor components of ⁽²⁾ was modeled by using the technique of cumulative atomic multipole moments (CAMMs).