Determination of extremely localized molecular orbitals in the framework of density functional theory

Extremely localized molecular orbitals are rigorously localized on only a preselected set of atoms and do not have any tails outside the localization region. The importance of these orbitals lies in their ability to be transferred from one molecule to another one. A new algorithm to determine extremely localized molecular orbitals in the framework of the density functional theory method is presented. This could also be a valuable tool in the quantum mechanics/molecular mechanics methodology where localized molecular orbitals are used to describe covalent bonds across the frontier region. The present approach is used to build up the electron density of thymopentin, a polypeptide constituted by five residues, starting from extremely localized molecular orbitals determined on a set of model molecules. The results obtained confirm good transferability properties for these orbitals.Proceedings of the 11th International Congress of Quantum Chemistry satellite meeting in honor of Jean-Louis Rivail     

EDTA—Cu配合物用于还原糖的测定

首次报道了应用ＥＤＴＡ（乙二胺四乙酸二钠盐）－铜配合物（ＥＣ）测定还原糖的分光光度法，结果表明，ｐＨ４～１１时ＥＣ的最大吸收波长为７３２ｎｍ，在ＨＣＯ－３ＣＯ２－３缓冲介质中，配合物ＥＣ的吸光度与还原糖在０７７～１６１ｍｇ（六碳糖）范围内有很好的线性关系，相关系数大于０９９８，样品测定回收率在９５％～１０５％之间。该法试剂易得、性质稳定，操作方便，灵敏度较高，取样量少于５ｍＬ。     

Theoretical studies of molecular conformation. Derivation of an additive procedure for the computation of intramolecular interaction energies. Comparison withab initio SCF computations

An additive procedure (SIBFA) is developed for the rapid computation of conformational energy variations in very large molecules. The macromolecule is built out of constitutive molecular fragments and the intramolecular energy is computed as a sum of interaction energies between the fragments. The electrostatic and the polarization components are calculated using multicenter multipole expansions of theab initio SCF electron density of the fragments. The repulsion component is obtained as a sum of bond and lone pair interactions.Tests of the procedure on a series of model compounds containing ether oxygens and pyridine-like nitrogens are reported and compared with the results of correspondingab initio SCF calculations. The resulting methodology is compatible with the simultaneous computation of intermolecular interactions.     

气相色谱叠加定量方法的研究

叠加法是由内标法衍生而来的一种气相色谱定量方法。对于较复杂混合物的分析,当选择内标物困难时,用叠加法定量更为方便。本文在大量实验的基础上,提出了叠加法定量过程中应注意的一些问题。     

<Emphasis Type="Italic">Ab initio</Emphasis> study of small coinage metal telluride clusters Au<Subscript>n</Subscript>Te<Subscript>m</Subscript> (<Emphasis Type="Italic">n,m</Emphasis> = 1, 2)

The geometries of the most stable isomers of gold telluride systems AuTe, Au₂Te, and AuTe₂ are determined using the MP2 method. The aspect of gold—telluride interaction, the electron correlation, and relativistic effects on geometry and stability are investigated at the MP2 and CCSD(T) theoretical levels. The results show that the electron correlation and relativistic effects are responsible not only for gold—gold attraction but also for additional gold—telluride interaction. The gold—telluride interaction is strong enough to modify the known pattern of bare gold clusters. Both effects are essential for determining the geometry and relative stability of this type of systems.     

2-苯基苯并咪唑衍生物非线性光学性质的从头算研究

采用HF／6-31G^*方法优化分子构型，在此基础上用CPHF方法系统地研究了多种基团取代的2-苯基苯并咪唑衍生物的二阶非线性光学系数βvec，并对βvdc的影响因素进行了探讨，为进一步设计综合性能优良的有机非线性光学材料提供理论指导．     

铁电极上硫脲及衍生物的缓蚀作用研究

用极化曲线方法测定了硫酸溶液中硫脲及其衍生物的浓度变化对铁腐蚀电化学行为的影响，获得了腐蚀电位下缓蚀剂对阴极和阳极过程的作用系数，用ＥＨＭＯ方法对硫脲及其衍生物的结构参数进行了量化计算，分析表明，缓蚀剂对阴极和阳极过程作用系数的大小与这些参量有密切关系。     

Errors involved in the activation energy calculated by integral methods when the frequency factor depends on the temperature ( A = A 0 T m)

The dependence of the frequency factor on the temperature (A=A ₀ T ^m) has been examined and the errors involved in the activation energy calculated from some integral methods without considering such dependence have been estimated. Investigated integral methods are the Coats-Redfern method, the Gorbachev-Lee-Beck method, the Wanjun-Yuwen method and the Junmeng-Fusheng method. The results have shown that the error in the determination of the activation energy calculated ignoring the dependence of the frequency factor on the temperature can be rather large and it is dependent on x=E/RT and the exponent m.     

Ternary surface complexes by theE(%)-pH curve method

A new method for the study of ternary surface complexes at liquid-solid interface, theE(%) -pH curve method, was proposed. Four types ofE(%)-pH curves, namely, phenomenon of left-right shifts of S-shaped curve, V-shaped curve, monodirection shift curve and X-shaped curve, were discovered. Correspondingly, apart from type (I) ternary surface complex and type (II) ternary surface complex , a new type of ternary surface complex was discovered. Project supported by the National Natural Science Foundation of China and the Fund of Doctoral Degree’s Spot.     

Novel polycationic biocides: Synthesis and antibacterial activity of polymeric phosphonium salts

Various polymeric phosphonium salts and the corresponding low-molecular-weight model compounds were prepared and their antibacterial activities against Staphylococcus aureus and Escherichia coli were explored by the viable cell counting method in sterile distilled water. Antibacterial activity of the polymers was found to be higher than that of the corresponding model compounds, particularly against S. aureus. Furthermore, the polymeric phosphonium salt exhibited a higher activity by 2 orders of magnitude than the polymeric quaternary ammonium salt with the same structure except the cationic part. Compounds with the longest alkyl chain (octyl) studied were found to exhibit particularly high activity, and this finding may be ascribed to the contribution of the increased hydrophobicity of the compounds to the cidal activity. © 1993 John Wiley & Sons, Inc.