1,2,4-三氮杂苯-(H2O)n复合物氢键相互作用的密度泛函理论研究

用密度泛函理论方法在B3LYP／6—31 G**水平上对1，2，4-三氮杂苯-(H2O)n(n=1，2，3)氢键复合物的基态进行了结构优化和能量计算，结果表明复合物之间存在较强的氢键作用，所有稳定复合物结构中形成一个N…H--O氢键并终止于弱O…H—C氢键的氢键水链的构型最稳定．同时，用含时密度泛函理论方法(TD—DPT)在TD—B3LYP／6—31 G**水平上计算了1,2，4-三氮杂苯单体及其氢键复合物的单重态第-1(n，π*)垂直激发能．     

含芯电子相关能修正的G2理论——G2(ful)

A general method in considering the core electronic correlation energies has been proposed and introduced into the standard Gaussian-2 (G2)[7] theory by small post-Hartree-Fock calculations. In this paper an additional MP2(FC)/6-31G(d) calculation over the G2 procedures is employed and examined in modification in modification to the flaw of Frozen-Core (FC) approximation of G2 vai eq.:
ΔE(full)= E[MP2(full)/6-31G(d)]-E[MP2(FC)/6-31G(d)]
where the MP2(full)/6-31G(d) energy has been obtained in the molecular geometry optimizations. This energy, ΔE(full), is directly added into the total G2 energy of a molecule in facilitating the effect of core electronic correlations for each molecule in chemical reactions. It has been shown that the over-all average absolute deviation for the 125 reaction energies of the G2 test set (test set 1) is slightly reduced from 5.09 to 5.01 kJ, mol(-1) while for the 55 D0 values, which have been used for the derivation of the A coefficient of the empirical High-Level...更多-Correction (HLC), it is also reduced from 4.99 [for both G2 and G2(COMPLETE)[8]]to 4.77 kJ• mol(-1). In addition, larger errors (greater than ±8.4 kJ•mol(-1) for the D0 energies are improved, especially for the largest error of the D0 of SO2 This error is reduced from 21.3 to 15.4 kJ. mol(-1), in which the experimental geometry would further reduce it by 7.1kJ.mol(-1)[8]. Another improvement is the absolute value of the A coefficient in HLC being reduced from 4.81 for G2 to 4.34 milli-hartrees which is believed to be useful in isolating the relationship between the HLC and the FC approximation. Modifications to the original G2 from this work is denoted as G2(fu 1) and thus the G2 (fu 1) total energy for a molecule is
E[G2(fu 1)]= E[G2]+Δ E(full)h
with a new ΔE[HLC] =-0.19α- 4.34nβ milli-hartree.     

多场耦合作用下光热敏感介电凝胶的力电耦合变形行为

介电弹性体在电场作用下将产生形变,为获得高的变形能,需对介电弹性体施以较强的电场,而强电场的施加可能诱发力电耦合失稳导致失效。针对光热敏感介电凝胶力电耦合变形行为,基于热力学和连续介质力学理论建立力电耦合变形模型,分析了光强、温度以及预拉伸对光热敏感介电凝胶力电耦合变形行为的影响,结果表明:无预拉伸时,随着电场强度的增大,光热敏感介电凝胶最终发生力电失稳,光强越小、温度越低发生力电失稳时的临界电压越高;预拉伸可显著改善力电稳定性,施加等双轴预拉伸后,凝胶厚度方向的伸长率显著变小,电场强度随电位移增大而线性增大,未出现力电失稳现象。     

Theoretical Study of the C_(60)O_3 Isomers

WiththepreparationandisolationofC,,O.'moreandmoreattentionwaspaidtotheirstructuresandpropertiest').WooddetectedC,,O.firstwhentheypreparedC,,byvaporizinggraphite").Fromthenon,thelaboratoriesallovertheworldhavepreparedC6,O.byvariousmethodssuchasPhotoxidationt2-4),Electrochemicaloxi-dation[si,Ozonizationt7.83andChemicaladditiont6'12-14iandsoon.Accordingtothefollow-uptheoreticalstudiesforC,,O.,itisindicatedthattherearetwoisomersofC,,O:eithertheoxygenatomislocatedoverthe6/6bondtogeneratethe6/…     

8－羟基喹啉纤维微柱分离富集ICP－AES测定多种痕量元素

制备了８－羟基喹啉纤维滤纸片，作为微柱填充物，同时富集了九种痕量元素，并分离了样品中的高盐组分。富集后的痕量组分采用电感耦合等离子体原子发射光谱法（ＩＣＰ－ＡＥＳ）测定，回收率为９０％～１０２％。     

非理想状态下的塔板理论模型

 在过程中 ,将流动相看成是由许多连续的塔板组成 ,每一塔板的高度与固定相塔板的高度相同。初始浓度的溶质被认为全部集中在流动相的第一塔板中 ;溶质在流动相和固定相之间动态分布。由于动力学因素的影响 ,当流动相流过一个塔板距离时 ,溶质不能够迅速地从固定相释放到流动相中 ,因此溶质在流动相和固定相中的分布浓度受到两个因素即反映系统热力学性质的分配系数P和反映系统动力学性质的释放概率因子α的影响。这一过程被认为是非理想状态下的过程。     

Studies on the Oxazaborolidine-catalyzed Enantioselective Reduction of 3-Morpholin-4-yl-1-phenyl-1-propanone with Density Functional Theory

Density functional theory (DFT) has been applied to study the enantioselective reduction of 3-morpholin-4-yl-l-phenyl-l-propanone with borane catalyzed by (S)-4-benzyl-5,5-diphenyl-l,3,2-oxazaborolidine at the B3LYP/6-31G* level. All molecular species involved in the four reaction steps have been fully optimized and the structural parameters are provided, and the micro process of reaction was also investigated. The catalyst-alkoxyborane adduct formed in step Ⅲ exhibits a B-O-B-N tetra-atomic ring. Reaction coordination calculations show that BH3 can react with 3-morpholin-4-yl-l-phenyl-l-propanone spontaneously, resulting in the need of 2 tool BH3 in the reaction.     

B20N20团簇的结构与稳定性

B3LYP/6-31G* density functional theory calculations have been carried out on the structure and stability of ten B20N20 clusters. It was found that two new proposed isomers with two octagons, twelve hexagons, eight squares in Cab and C2 symmetry were more stable than the isomer with sixteen hexagons and six squares in C2 symmetry which was previously deemed to the most stable by 79.5 and 13.8 kJ/mol respectively. The isomer with two decagons in S10 symmetry is much higher in energy than the most stable structure in C4h symmetry by 637.2 kJ/mol.     

CH4, CO2和H2O在非金属原子修饰石墨烯表面的吸附

煤层气(矿井瓦斯)是一种有望替代传统化石燃料，如煤、石油和天然气的非常规气体. 作为可得的清洁能源，它的利用被认为是节能和经济的选择. 在本工作中，非金属原子X(X=H，O，N，S，P，Si，F，Cl)修饰的石墨烯(Gr)被用来代表具有结构异性的煤表面模型. 通过密度泛函理论系统地研究了煤层气组分Y(Y=CH₄，CO₂，H₂O)在非金属原子修饰石墨烯上的吸附作用. 结果表明Y在非金属原子修饰石墨烯上的吸附均为物理吸附. 态密度和差分电荷密度共同表明了这种弱的相互作用.其中，H和Cl对CH₄的作用较大； N、O、F、Cl对CO₂的作用较强； N，Cl对H₂O的影响不容忽视. 总的来说，吸附能大小依次为：H₂O>CO₂>CH₄. 因此，在CH₄富集的煤层里注入H₂O或CO₂可以与CH₄形成竞争吸附，进而提高煤层气采收率. 本工作提供了在分子水平下煤层气与非金属原子修饰石墨烯之间的相互作用的详情，并为煤层瓦斯的开采与分离提供了有用的信息.     

光纤松耦合型传感器特性研究

本文介绍一种实用的光纤传感器,它由二根光纤或多根光纤紧靠一起,并在同一位置除去局部包层,成为松耦合状态,在这种状态下,研究了它的特性和应用。 当耦合间隙中充满某种液体介质时,耦合效率明显增大,因此可以方便地判别该介质是否存在。并且实验证明了一种光纤只能有一种相近于光纤芯子折射率的介质具有最大的灵敏度。当间隙内的介质不变时,耦合功率的大小决定于耦合距离d和耦合长度l,l一旦决定以后,d的调节精度为0.1mm量级,易于在机械结构上实现线性检测。