泛函数迭代法求解反胶束内双电层电势

用泛函数分析理论中的迭代法求解了反胶束内关于双电层势的Poisson- Boltzmann（PB）方程，导出了泛电位下的第一、二次迭代的解析表达式。与 Debye-Huckel（DH）线性近似及计算机的数值解进行对比表明，迭代解不仅在低电 位条件下能与两者相符合，而且在高电位下与数值解在相吻合。     

粘土胶体表面双电层重叠时ψδ及ψd的计算

本文依据Gouy-Chapman双电层理论导出了描叙粘土胶体表面压电层重叠时对阴离子负吸附方程。以实验为基础, 利用该方程通过计算机数值解解出粘土胶体表面外Helmhotz面(OHP)处的电位ψ_δ和两粘粒之间的中点电位ψ_d, 并对所得结果进行了讨论。     

冲洗色谱特征点法测定表面分形维数初探

在用非线性气相色谱测填料表面分形维数中,首次运用气固色谱（ＥＣＰ法（ｅｌｕｔｉｏｎ ｂｙ ｃｈａｒａｃｔｅｒｉｓｔｉｃ ｐｏｉｎｔｓ ｍｅｔｈｏｄ）,测定了正戊烷、正已烷、正庚烷３种烷烃在不同颗粒大小的硅胶表面的吸附等温线,通过拟合Ｌａｎｇｍｕｉｒ方程,求出单分子饱和吸附容量,并采用单分子层吸附的分形模型,求得硅胶的发形维数,提供了一种测定表面分形维数的新方法。     

纳米氧化锌的机械力化学表面改性

采用机械力化学表面改性工艺,以硬脂酸为改性剂,在气流粉碎机中对纳米氧化锌进行解团聚和表面改性,并借助SEM、XRD、FF—IR和XPS对改性前后的氧化锌粉体进行结构表征．结果表明：硬脂酸分子化学键合在氧化锌表面．改性前后氧化锌的晶体结构相同,其颗粒的团聚性降低,二次粒径明显减小．通过测定改性样品的活化指数和亲油化度,选择最佳的改性剂用量为氧化锌质量的10％,氧化锌表面亲油疏水,在有机溶剂中有较好的分散性．     

双电层相互作用时胶体表面电位的分布及电荷密度的计算

本文以实验为基础,运用计算机数值解解出双电层相互作用时平面胶体表面电位ψ随距离X的分布,依据作者导出的双电层相互作用时胶体表面阴离子负吸附方程,计算出胶体表面外Hclmhotz面(OHP)处的表面电荷密度σ_δ;讨论了双电层相互作用程度(ψ_d/ψ_δ)对胶体表面电位分布及其表面电荷密度的影响。     

碱性水溶液中甲醛在硅电极表面的电化学行为及其对硅化学刻蚀的影响

研究了KOH水溶液中氧化剂甲醛在p-Si和n-Si(100)单晶半导体电极表面的电化学行为及其对硅化学刻蚀表面形貌的影响．实验结果表明，甲醛不仅影响p-和n-型半导体电极在碱性溶液中的阳极氧化峰电流，而且在负电位区能在Si(100)电极上发生还原．在光照条件下，p-Si(100)电极上也观测到了HCHO的电化学还原及光电流倍增效应．甲醛在硅电极表面的电化学还原反应分两步进行，反应终产物为甲醇．此外，HCHO能有效抑制碱性溶液中Si表面“金字塔”型表面粗糙颗粒的形成。     

平板型高电位胶粒双电层的相互作用

利用线性迭加法,提出了平行平板型高电位颗粒之间的弱相互作用的近似表达式.结合文献[3]给出的强相互作用表达式,对高电位平行平板型颗粒的相互作用给出了完整的描述,和精确数值解吻合相当好.强弱相互作用的接合点在κh=4,误差在接合点处最大,～10％.根据Derjaguin法和改进的Derjaguin法,求出了高电位球颗粒在恒电位条件下的相互作用能.     

泛函数法研究柱状反胶束双电层

利用泛函数分析理论中的迭代方法, 建立并在泛电位下求解了柱状反胶束水池内关于双电层电位的Poisson-Boltzmann (PB)方程, 推导出了该方程的第一、二次迭代解及电荷密度表达式, 并将其与Debye-Hückel(DH)的低电位线性近似方法得到的结果进行了比较.     

基于原子表面的蛋白质水合自由能预测模型

提出了一种计算蛋白质水合自由能的简化模型（SAWSA 2）.模型把蛋白质分子中的原子分为20种不同的原子类型,通过每类原子的溶剂可及化表面以及相应的溶剂化参数,就可以得到分子的水合自由能.不同原子类型的溶剂化参数通过110个蛋白质分子水合自由能拟合得到,水合自由能的标准值采用了基于求解Possion-Boltzmann方程（PB）以及分子表面计算（SA） 相结合的方法.采用得到的模型,预测了20个蛋白质分子的水合自由能,预测值的相对值和绝对值都能和PB/SA的计算值很好地吻合,大大优于两种已报导的水合自由能模型.     

Brij类表面活性剂与Laponite纳米颗粒的相互作用及其稳定乳液的研究

通过表面张力、Zeta电位和流变学参数的测定, 研究了聚氧乙烯烷基醚类非离子型表面活性剂(Brij 30和Brij 35)在合成锂皂石(Laponite)纳米颗粒表面的吸附及对Laponite水分散体系中颗粒间相互作用和体系粘度的影响. 结果表明, 这类表面活性剂能显著地吸附在Laponite颗粒表面上, 且吸附量随其分子中POE链长短而不同. 这种吸附没有改变Laponite粒子的带电性质, 但一定程度地降低了Laponite颗粒Zeta电位; 吸附也会减弱颗粒间的相互作用, 降低体系的粘度. 实验以Laponite和Brij为乳化剂, 制备了O/W型乳状液. 乳液稳定性变化和乳液粒径分布结果表明, 体系中Brij的浓度较低时, 乳液的性质主要是由Laponite颗粒决定的; 而Brij浓度较高时, 则主要取决于Brij表面活性剂. 高速剪切含Brij的Laponite水分散体系, 剪切后表面张力随时间的变化表明, 剪切作用会使得吸附在Laponite颗粒表面的Brij分子不同程度地解吸下来. 这也意味着乳液制备时, 高速剪切作用也会造成Brij分子自Laponite颗粒表面的脱附, 这可能是非离子表面活性剂与阳离子表面活性剂对负电固体颗粒稳定乳液影响不同的原因.     

Electronics states of a surface nickel atom on the nickel (001) surface

Electronic states of a Ni(001) surface atom, corresponding to different d-occupations, are calculated for a 49 atom cluster model of the surface. SCF and CI calculations on a variety of low lying states are reported. Strong mixing between d⁹ and d¹⁰ configurations is found for the lowest states of different symmetries with the splitting between the states ranging from 1.7 to 2.0 eV. In contrast, the d⁸ configurations do not interact strongly with other d configurations and lie energetically much higher at 3.0 eV. Thus, the splitting between d⁹ and d¹⁰ configurations is comparable to that of the isolated atom whereas the d⁸ configuration is greatly destabilized. The cluster produces a manifold of closely spaced electronic states above the ground state thus modeling the density of unoccupied states above the Fermi level.     

Cu ion core conservation from reactant to product in the Cu+F2 chemiluminescent reaction

Electronic chemiluminescence from the reaction of selected ground state (²S_1/2) or metastable (²D_5/2, ²D_3/2) copper atoms with fluorine has been studied using a hollow cathode-flowing afterglow reactor. The observed signal related to the Cu(²S) and Cu*(²D) atom densities, indicate that the chemiluminescence cross-section for Cu*(²D) atoms is about 10⁴ times larger than for Cu(²S) atoms. This strong propensity is explained in terms of a direct reaction, initiated by a harpooning process, during which the Cu⁺ ion core of the reactant (3d¹⁰ for Cu(²S) and 3d⁹4s for Cu*(²D)) is conserved in the products (ionic structure Cu⁺(3d¹⁰)F⁻ for the CuF ground state and Cu⁺(3d⁹4s)F⁻ for the CuF*(a, A, B, C, D) chemiluminescent states).     

Comparative studies on excitation of nickel ionic lines between argon and krypton glow discharge plasmas

The emission characteristics of nickel ionic lines in a glow discharge plasma are investigated when argon or krypton was employed as the plasma gas. Large difference in the relative intensities of nickel ionic lines which are assigned to the 3d⁸4p–3d⁸4s transition is observed between the krypton plasma and the argon plasma. Different intense Ni II lines appear in the krypton spectrum and in the argon spectrum, such as the Ni II 231.601 nm for Kr and the Ni II 230.009 nm for Ar. The excitation energy of these Ni II emission lines can give a key in considering their excitation mechanisms. The explanation for these experimental results is that charge-transfer collisions between nickel atom and the plasma gas ion play a major role in exciting the 3d⁸4p excited levels of nickel ion. The conditions for energy resonance in the charge-transfer collision determine particular energy levels having much larger population; for example, the 3d⁸4p ⁴D_7/2 level (6.39 eV) for Kr and the 3d⁸4p ⁴P_5/2 level (8.25 eV) for Ar.     

Study on the Radius of an Electrical Spherical Micelle： Functional Theoretical Approach

For the purpose of eliminating restriction, the Poisson-Bokzmann (PB) equation, which represents the potential of the electrical double layer of spherical miceUes, can be solved analytically only under the lower potential condition, a kind of iterative method in functional analysis theory has been used. The radius of the spherical particle can be obtained from the diagram of the second iterative solution of the potential versus the distance from the center of the particle. The influences of the concentration of the ions, the charge number of ions, the aggregation number of the particle, the dielectric constant of solvent and the temperature of system on the radius also have been studied.     

A Selective and Sensitive Fluorescence Probe for Se(Ⅳ) Based on Fluorescence Quenching of Gatifloxacin

A novel high selective and sensitive fluorescence probe termed gatifloxacin was discovered based on fluorescence "on-off" phenomenon in the presence of Se(Ⅳ). In the Tris-HCl/acetonitrile(3:7, volume ratio, Tris-HCl 0.05 mol/L, pH=7.3) sys-tem, the fluorescence intensity of gatifloxacin was linearly decreased with the concentration increase of Se(Ⅳ) in a range of 1.0×10^-5-5.0×10^-5 mol/L with a correlation coefficient of 0.9979(R²=0.9958) and in a range of 5.0×10^-5-1.0×10^-4 mol/L with a correlation coefficient of 0.9973(R²=0.9946). The detection limit of Se(Ⅳ) was 1.70×10^-6 mol/L.     

Electrochemical Behavior of Mitoxantrone and Its Determination at a Pt／C Implanted Modified Microelectrode

In a 0.02 mol/L Na2HPO4-KH2PO4(PBS) buffer solution(pH=6.82), the electrochemical behavior of mitoxantrone was studied by linear-sweep voltammetry and cyclic voltammetry at a Pt/C ion implantation modified microelectrode. A sensitive reduction peak was observed. The peak potential was -0.72 V(vs.SCE), the peak current was proportional to the concentration of mitoxantrone within the ranges of 7.0×10-8-9.0×10-7 mol/L and 1.0×10-6-2.4×10-5 mol/L, with a detection limit of 4.0×10-8 mol/L. The linear correlation coefficients were 0.9994 and 0.9992, respectively. This method has been applied to the direct determination of mitoxantrone in simulated urine. The recoveries were in the range from 96.2% to 105.9%. The reduction process was a quasi-reversible one with adsorptive characteristics at the Pt/C microelectrode. The electrode reaction rate constant ks and the electron transfer coefficient α of the system were determined to be 4.5 and 0.65 s-1, respectively. The experiments showed that Pt element had surely been implanted into the surface of the carbon fiber, and the atomic Pt improved the electrocatalytic activity. The Pt/C microelectrode had a good stability and reproducibility.     

CO2势能面和振动激发态的理论研究

采用振动自洽场-组态相互作用(SCF-CI)方法通过实验振动光谱优化了CO₂分子的势能函数,由该势能函数计算得到的纯振动光谱数据与实验值相比,所有能级的误差均在4cm^-1以内,均方根偏差为1.50cm^-1,所预测的Π态振转光谱也与实验值很接近.     

过渡金属复合氧化物电子组态与表面光伏响应的关系(Ⅰ)──M(Ⅱ)铁酸盐(M=Cu,Co,Ni)的研究

利用表面光电压谱及场诱导表面光电压谱研究了部分过渡金属复合氧化物的电子组态与其光伏响应的关系.结果表明,在过渡金属M(M＝Cu,Co,Ni)铁酸盐系列样品中,开壳层的Cu(Ⅱ)(铁酸盐)和CO(Ⅱ)(铁酸盐)的电荷转移跃迁(CT)具有双激发态的成分,其中含有较强的低能电子跃迁;与它们相比,闭壳层的Ni(Ⅱ)铁酸盐的CT跃迁则需要较大的能量.三者的FISPS证实了它们具有不同的CT跃迁性质,为其催化反应机理研究提供了微观信息.     

EPR lineshape studies of low-temperature vanadium 3d polaron dynamics in the 70V2O5-30P2O5 binary glass

In a specimen of 70V₂O₅-30P₂O₅glass, EPR lineshapes of the vanadium 3d¹ polaron have been studied between 4 and 77 K. At the lowest temperature the unpaired electron is localized at a single ⁵¹V site, and values of g=1.959, g= 1.989, A = 156.6 × 10⁻⁴ cm⁻¹ and A=53.8 × 10⁻⁴ cm⁻¹ have been measured. A Markovian small-step rotational diffusion model consistent with the random structure of the glass network is proposed for the polaron dynamics at the higher temperatures up to 77 K. This motion has a small activation energy barrier of 114 μeV.     

d3(Re+4)和d4(Os+4)组态晶体能谱的配位场理论分析

本文根据文献[4]提出的配位场理论方法,采用SLГ_SГtτ方案,对晶体K₂PtCl₆中Re⁺⁴(5d³)和Os⁺⁴(5d⁴)离子能谱进行全分析,考虑了全部d³和d⁴组态的静电作用能,正八面体场势能和旋轨偶合作用能,计算了能级随参数变化曲线,能谱理论计算结果与文献[9-10]强场方案计算结果一致,但改正了前人对实验能谱指认不正确之处。