(λ,μ)-凸泛函的一条重要性质

本文定义了（λ，μ）-凸泛函的概念，并在赋β-范空间上得出了这类泛函的一条重要性质．关键词##4（λ，μ）-凸泛函，凸泛函。

关于C^(1-0)泛函的极小极大原理的一个注记

用非光滑分析的思想,对C^(1-0)泛函进行了分析,得到了关于C^(1-0)泛函的几个极小极大定理。

关于赋β-范空间上α-凸泛函的一条重要性质

给出了α-凸泛函的概念,并在赋β-范空间上得出了α-凸泛函的一条重要性质。

赋β-范空间上(λ,μ)-凸泛函族的共鸣定理

文章首先说明-凸泛函是一类非常具有普遍性的非线性泛函，接着在第二纲的赋-范空 间上，对-凸泛函族，建立起共鸣定理的两种基本形式. 由于-凸泛函的广泛性和定理形式的 一般性，共鸣定理的这种形式在凸体理论等研究领域具有广泛的应用.

含时密度泛函理论-电子圆二色谱(TDDFT ECD)计算法在判定天然产物绝对构型中的应用

天然产物结构鉴定过程中其立体构型的判定始终是最具有挑战性的一个环节。在解决天然产物立体化学问题的众多方法中,利用化合物的电子圆二色谱(ECD)图确定其绝对构型是一个快速、有效而可靠的方法。近年来随着量子化学计算法的发展,含时密度泛函理论-ECD(TDDFT ECD)技术逐渐成为化学家用于判定天然产物绝对构型的一种有力手段。根据适用对象的差别,该技术可分为固态TDDFT ECD计算与液态TDDFT ECD计算两种方法。两种方法在应用中均十分直观、明了,简言之是将实测ECD谱图与计算ECD谱图进行比对,二者吻合度越高则判定结果越可靠。受篇幅限制,本文简介TDDFT ECD计算法的原理,并选取几个实例以说明该方法的应用范围。

Microthermokinetic study of xanthate adsorption on impurity-doped galena

Six kinds of galena with different impurities were synthesized and the effects of impurities on the floatability of galena were investigated. The thermodynamic and kinetic parameters on the galena surface were measured using microcalorimetry, and the adsorption configuration and energy of butyl xanthate on the surfaces of galena with different impurities were simulated by density functional theory. Flotation experiments showed that Ag and Bi significantly promoted the recovery of galena, while Zn, Sb, Mn, and Cu reduced the recovery of the flotation. Microthermokinetic results indicated that the absolute value of xanthate adsorption heat was directly proportional to the flotation recovery of galena. Adsorption heat and reaction rate coefficients of xanthate on galena containing Ag or Bi were larger than those on pure galena, but smaller on galena containing Cu or Sb. Additionally, the relationship between the heat of unsaturated adsorption of xanthate and the adsorption energy of impurity atom on galena surface was investigated.

Flotation behavior and adsorption mechanism of(1-hydroxy-2-methyl-2-octenyl) phosphonic acid to cassiterite

The flotation behavior and adsorption mechanism of novel（1-hydroxy-2-methyl-2-octenyl） phosphonic acid（HEPA） to cassiterite were investigated by micro-flotation tests, zeta potential measurements, FTIR determination and density functional theory（DFT） calculation. The flotation results demonstrated that HEPA exhibited superior collecting performance compared with styrene phosphonic acid（SPA）. The cassiterite recovery maintained above 90% over a wide pH range of 2-9 with 50 mg/L HEPA. The results of zeta potential measurement and FTIR detection indicated that the adsorption of HEPA onto cassiterite was mainly attributed to the chemisorption between HEPA monoanions and Sn species on mineral surfaces. The DFT calculation results demonstrated that HEPA monoanions owned higher HOMO energy and exhibited a better affinity to cassiterite than SPA, which provided very clear evidence for the stronger collecting power of HEPA presented in floatation test and zeta potential measurement.

Adsorption mechanism of 2-mercaptobenzothiazole on chalcopyrite and sphalerite surfaces:Ab initio and spectroscopy studies

Interaction mechanism of the collector,2-mercaptobenzothiazole（MBT）,with chalcopyrite and sphalerite surfaces were investigated by Fourier transform infrared（FTIR） and density functional theory,Results of FTIR showed that some characteristic peaks of MBT were observed on the chalcopyrite surface,including C=N,C=N-S and C-S stretching vibration peaks,and the adsorption product was CuMBT.But there were no characteristic peaks of MBT on the sphalerite surface.The thione molecular form of MBT was the most efficient and stable,N and exocyclic S were the more favourable reactive sites for nucleophilic attacked by metal atoms.Compared with ZnS（110）,MBT is more readily adsorbed on CuFeS2（112）.Attachment of MBT occurs due to strong bonding through exocyclic S p and s orbits with Cu d orbit on CuFeS2（112） and electron transfer from Cu atom to S atom.Under the vacuum condition,MBT in the form of thione molecular cannot be adsorbed on ZnS（110） spontaneously.

Density Function Theory Study on Effects of Different Energetic Substituent Groups and Bridge Groups on Performance of Carbon-Linked Ditetrazole 2N-Oxides

Based on the parent tetrazole 2N-oxide, six series of novel carbon-linked ditetrazole 2N- oxides with different energetic substituent groups （-NH2, -Na, -NO2, NF2, -NHNO2） and energetic bridge groups （-CH2-, -CH2-CH2-, -NH-, -N=N-, -NH-NH-） were designed. The overall performance and the effects of different energetic substituent groups and energetic bridge groups on the performance were investigated by density functional theory and electrostatic potential methods. The results showed that most of designed compounds have oxygen balance around zero, high heats of formation, high density, high energy, and acceptable sensitivity, indicating that tetrazole N-oxide is a useful parent energetic compound employed for obtaining high energy compounds, even only combined with some very common energetic substituent groups and bridge groups. Comprehensively considering the effects on energy and sensitivity, the -NO2, -NF2, -NH- and-NH-NH- are appropriate substituent groups for combining tetrozale N-oxide to design new energetic compounds, while -NH2, -Na, -CH2-CH2-, and -N=N- are inappropriate.

Framework-solvent interactional mechanism and effect of NMP/DMF on solvothermal synthesis of [Zn_4O(BDC)_3]_8

In order to explore the effect mechanism of solvent on the synthesis of the metal organic framework materials, the microscopic interaction between solvent and framework and the effects of N,N-dimethyl-formamide(DMF) or N-methyl- 2-pyrrolidone(NMP) on solvothermal synthesis of [Zn4O(BDC)3]8 were investigated through a combined DFT and experimental study. XRD and SEM showed that the absorbability of NMP in the pore of [Zn4O(BDC)3]8 was weaker than that of DMF. The thermal decomposition temperature of [Zn4O(BDC)3]8 synthesized in DMF was higher than that in NMP according to TG and FT-IR. In addition, the nitrogen sorption isotherms indicated that NMP improved gas sorption property of [Zn4O(BDC)3]8. The COSMO optimized calculations indicated that the total energy of Zn4O(BDC)3 in NMP was higher than that in DMF, and compared with non-solvent system, the charge of zinc atoms decreased and the charge value was the smallest in NMP. Furthermore, the interaction of DMF, NMP or DEF in [Zn4O(BDC)3]8 crystal model was calculated by DFT method. The results suggested that NMP should be easier to be removed from pore of materials than DMF from the point of view of energy state. It can be concluded that NMP was a favorable solvent to synthesize [Zn4O(BDC)3]8 and the microscopic mechanism was that the binding force between Zn4O(BDC)3 and NMP molecule was weaker than DMF.

Application of PCA and HCA to the Structure-Activity Relationship Study of Fluoroquinolones

Density functional theory （DFT） was used to calculate molecular descriptors （properties） for 12 fluoro-quinolone with anti-S.pneumoniae activity. Principal component analysis （PCA） and hierarchical cluster analysis （HCA） were employed to reduce dimensionality and investigate in which variables should be more effective for classifying fluoroquinolones according to their degree of an-S.pneumoniae activity. The PCA results showed that the variables ELUMO, Q3, Q5, QA, logP, MR, VOL and △EHL of these compounds were responsible for the anti-S.pneumoniae activity. The HCA results were similar to those obtained with PCA.The methodologies of PCA and HCA provide a reliable rule for classifying new fluoroquinolones with antiS.pneumoniae activity. By using the chemometric results, 6 synthetic compounds were analyzed through the PCA and HCA and two of them are proposed as active molecules with anti-S.pneumoniae, which is consistent with the results of clinic experiments.

ADAPTIVE PREDICTIVE CONTROL OF NEAR-SPACE VEHICLE USING FUNCTIONAL LINK NETWORK

A novel nonlinear adaptive control method is presented for a near-space hypersonic vehicle （NHV） in the presence of strong uncertainties and disturbances. The control law consists of the optimal generalized predictive controller （OGPC） and the functional link network （FLN） direct adaptive law. OGPC is a continuous-time nonlinear predictive control law. The FLN adaptive law is used to offset the unknown uncertainties and disturbances in a flight through the online learning. The learning process does not need any offline training phase. The stability analyses of the NHV close-loop system are provided and it is proved that the system error and the weight learning error are uniformly ultimately hounded. Simulation results show the satisfactory performance of the con- troller for the attitude tracking.

Ab initio Study of Complexation Process between Poly（amido-amine） and Nano-Silicon Dioxide

To understand better the molecular-level details of ≡Si＋ （SC） or ≡SiO- （SOA） ion group to -NH2 teminated poly（amido-amine） dendrimers in the gas phase, density functional theory is used to optimize the minimum energy and transition state structures with UB3LYP/6- 311G（d） and HF/6-31G levels. The tertiary amine nitrogen and the amide oxygen are found to be the most favorable binding sites. The activation energies of the different active sites and the reaction steps of SC and/or SOA ion group and the amide sites are also analyzed. The stable compounds are formed via the electrostatic interaction and the coordination effect. The orientation of the amide O and the rotation of the branches minimizes the energy of the whole system.

DFT Study of Alkali Metal Atom Adsorption on Defect-Free MgO（001）Surface

The adsorption of isolated alkali metal atoms （Li, Na, K, Rb, and Cs） on defect-free sur- face of MgO（001） has been systemically investigated with density functional theory using a pseudopotential plane-wave approach. The adsorption energy calculated is about -0.72 eV for the lithium on top of the surface O site and about one third of this value for the other alkali metals. The relatively strong interaction of Li with the surface O can be explained by a more covalent bonding involved, evidenced by results of both the projected density of states and the charge density difference. The bonding mechanism is discussed in detail for all alkali metals.

Density Functional Study of AunCo （n=1-7）

Cobalt-doped gold clusters AunCo （n=1-7） are systematically investigated for the possible stable geometrical configurations and relative stabilities of the lowest-lying isomers using density-functional theory at B3LYP/LanL2DZ level. Several low-lying isomers were determined, and many of them are in electronic configurations with a high spin multiplicity. The results indicate that the ground-state AunCo（n=1-7） clusters adopt a planar structure except for n=7. The stability trend of the AunCo （n=1-7） clusters shows that the Au2Co clusters are magic cluster with high stability.

Electronic Structures, DNA-binding, SAR, and Spectral Properties of Ruthenium Methylimidazole Complexes [Ru（MeIm）4L]^2＋（L=iip,tip,2ntz）

Theoretical studies on the electronic and geometric structures, the trend in DNA-binding affinities as well as the the structure-activity relationship （SAR） of a series of water-soluble Ru（II） methylimidazole complexes, i.e. [Ru（Mehn）4iip]^2＋ （1） （MeIm=l-methylimidazole, iip=2-（1H-imidazo-4-group）-lH-imidazo[n,5-f][1,10]phenanthroline）, [Ru（MeIm）4tip]^2＋ （2） （tip=2-（thiophene-2-group）-lH-imidazo[4,5-f] [i,10]phenanthroline）, and [Ru（Melm）42ntz]^2＋ （3） （2ntz=2-（2-nitro-l,3-thiazole-5-group）-lH-imidazo[4,5-f][1,10]phenanthroline）, were car- ried out using the density functional theory （DFT）. The electronic structures of these Ru（II） complexes were analyzed on the basis of their geometric structures optimized in aqueous solution, and the trend in the DNA-binding constants （Kb） was reasonably explained. The results show that the replacement of imidazole ligand by thiophene ligand can effectively improve the DNA-binding affinity of the complex. Meanwhile, it was found that introduc- ing the stronger electronegative N atom and NO2 group on terminal loop of intercalative ligand can obviously reduce the complex＇s LUMO and HOMO-LUMO gap energies. Based on these findings, the designed complex [Ru（MeIm）42ntz]^2＋ （3） can be expected to have the greatest Kb value in complexes 1-3. In addition, the structure-activity relationships and antitumor mechanism were also carefully discussed, and the antimetastatic activity of the designed complex 3 was predicted. Finally, the electronic absorption spectra of this series of complexes in aqueous solution were calculated, simulated and assigned using DFT/TDDFT methods as well as conductor-like polarizable continuum model （CPCM）, and were in good agreement with the experimental results.

一类推广的Bernstein-Kantorovich算子在Orlicz空间内的逼近

该文根据Bernstein-Kantorovich算子的有关性质,讨论了Bernstein-Kantorovich的Sikkema-Bezier变形算子在Orlicz空间内逼近的有关结论 .

Theoretical Study of the C-CI Bond Dissociation Enthalpy and Electronic Structure of Substituted Chlorobenzene Compounds

Quantum chemical calculations were used to estimate the bond dissociation energies （BDEs） for 13 substituted chlorobenzene compounds. These compounds were studied by the hybrid density functional theory （B3LYP, B3PW91, B3P86） methods together with 6-31G^＊＊ and 6-311G^＊＊ basis sets. The results show that B3P86/6-311G^＊＊ method is the best method to compute the reliable BDEs for substituted chlorobenzene compounds which contain the C-C1 bond. It is found that the C-C1 BDE depends strongly on the computational method and the basis sets used. Substituent effect on the C-C1 BDE of substituted chlorobenzene compounds is further discussed. It is noted that the effects of substitution on the C-C1 BDE of substituted chlorobenzene compounds are very insignificant. The energy gaps between the HOMO and LUMO of studied compounds estimate the relative thermal stability ordering are also investigated and from this data we of substituted chlorobenzene compounds.

叠氮桥对双核镍配合物磁性影响的密度泛函理论研究

结合对称性破损(BS)方法,采用不同的密度泛函理论(DFT)对反铁磁性μ-1,3-N3-Ni(II)叠氮配合物[LNi2(N3)](Cl O4)2(L=pyrazolate)的磁特性进行了研究.结果显示,杂化密度泛函理论(HDFT)的计算结果与实验数据非常吻合,能够准确描述配合物的磁特性.磁轨道研究结果表明,配合物表现出较大的单占据轨道能量劈裂(0.93-0.99 e V),显示配合物的单占据轨道去简并化程度较大,且配合物中的2个磁通道(叠氮基、配体pyrazolate)中都分别存在有氮原子之间的p轨道重叠,这些都使得体系表现为反铁磁耦合作用.另外,配合物的磁性与叠氮桥和两金属离子间形成的二面角(τ,Ni-N-N-N-Ni)密切相关,τ从-55.38°逐渐变化到-1.5°的过程中,其反铁磁性逐渐增强,交换耦合常数(Jab)的绝对值逐渐增大,并在-11.95°处达到最大值(Jab=-151.02 cm-1).在此过程中,配合物中叠氮桥及其所连接的2个Ni离子与pyrazolate基配体L-中的2个桥原子N(4)、N(5)形成的七元环共平面性不断增强,即共平面性会诱导增强体系的反铁磁相互作用.

Modeling Photovoltaic Performances of BTBPD-PC61BM System via Density Functional Theory Calculations

Designing and fabricating high-performance photovoltaic devices have remained a major challenge in organic solar cell technologies. In this work, the photovoltaic performances of BTBPD-PC61BM system were theoretically investigated by means of density functional theory calculations coupled with the Marcus charge transfer model in order to seek novel photovoltaic systems. Moreover, the hole-transfer properties of BTBPD thin-film were also studied by an amorphous cell with 100 BTBPD molecules. Results revealed that the BTBPD- PC61BM system possessed a middle-sized open-circuit voltage of 0.70 V, large short-circuit current density of 16.874 mA/cm2, large fill factor of 0.846, and high power conversion effi- ciency of 10%. With the Marcus model, the charge-dissociation rate constant was predicted to be as fast as 3.079×10^13 s^-1 in the BTBPD-PC61BM interface, which was as 3-5 orders of magnitude large as the decay （radiative and non-radiative） rate constant （108-10^10 s^-1）, indicating very high charge-dissociation efficiency （-100%） in the BTBPD-PC61BM system. Furthermore, by the molecular dynamics simulation, the hole mobility for BTBPD thin-film was predicted to be as high as 3.970× 10^-3 cm^2V^-1s^-1, which can be attributed to its tight packing in solid state.