Off‐atomic site charges in some anions,metal cations,and complexes: Significance for electrostatic properties and binding

Electronic structures and properties of several anions, metal cations, and their complexes with neutral molecules were investigated at the HF/6‐31G** and B3LYP/6‐31G** levels of theory. Charges shifted from atomic sites due to atomic orbital hybridization called hybridization displacement charges (HDC) were investigated in detail. It has been found that many components of HDC are associated with each atom of ion that are shifted from the atomic sites, those associated with metal cations being shifted by large distances as found previously in electrically neutral systems. It is shown that atomic orbitals are appreciably rehybridized in going from neutral molecules to anions and cations. Molecular dipole moments and surface molecular electrostatic potentials (MEP) are obtained satisfactorily using HDC for the various types of species mentioned above. In the OH^?? H₂O complex, reversal of direction of shift of an HDC component associated with the hydrogen atom of H₂O involved in hydrogen bonding, indicates that the hydrogen bond between OH^? and H₂O would have some covalent character. Other atomic site‐based point charge models cannot provide such information about the nature of bonding. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem 2007     

Electrical Double Layer on Liquid Bi–Ga Alloys in Aqueous Solutions

Double-layer characteristics of a liquid bismuth–gallium electrode are studied in aqueous electrolyte solutions. Based on the results obtained it is shown that Bi in an alloy with Ga is a surface-active component and forced out to the electrode surface layer. For electrode charges q –5 C/cm², the double layer characteristics of Bi–Ga electrodes approach those of a bismuth electrode. Thus, with respect to its electrochemical properties, a Bi–Ga electrode containing 0.25 at. % Bi simulates a liquid bismuth electrode. The corrected electrochemical work function is determined for bismuth. The close values of the difference of zero-charge potentials on mercury and bismuth in water and the difference of corrected electrochemical work functions for these metals points to the very low hydrophilicity of the Bi–Ga electrode, which approaches the value for mercury at negative electrode potentials. Taking into account that the Bi–Ga electrode displays no semimetallic properties, the similarity of the electric double layer (EDL) parameters for the Bi–Ga alloy and solid pure Bi indicates that the semimetallic properties of bismuth make no contribution to the EDL characteristics of the alloy in the studied range of negative charges q –5 C/cm².     

Direct current conductivity and ion motions in poly(vinyl chloride)‐poly‐1,4‐cis butadiene blends by electrical relaxation method

Ionic conduction in poly(vinyl chloride) (PVC)‐poly‐1,4‐cis butadiene blends has been studied using the electrical relaxation method. Temperature dependence of direct current (dc) conductivity does not change at the glass transition of PVC but does change at higher temperatures. The shape of the frequency dispersion curve of the electric modulus in a frequency range from 0.01 to 100 Hz depends on temperature. At low temperatures, the shape of the dispersion curve is reproduced by calculation assuming the Debye decay function, whereas this is not reproduced at high temperatures. Two kinds of analysis of the dispersion curve are discussed for this complicated change in the shape of the dispersion. One is that the dispersion curve is regarded as a single process expressed by the Kohlrausch decay function, and the other is that the curve is regarded as two processes expressed by the Debye and the Kohlrausch decay functions. The observed dispersion of the electric modulus is not expressed by the single process but by the two processes. One of the two processes is characterized by the Debye decay function, and the other is characterized by the Kohlrausch decay function. The parameter of the Kohlrausch decay function for one of these processes has a value of 0.82, and this value does not depend on temperature. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 40: 226–235, 2002     

Linear viscoelastic properties of electro-rheological nano-suspension confined to narrow gap between electrodes

The linear viscoelastic properties of a suspension composed of titanium dioxide nanoparticles were measured under the direct current (dc) electric field with narrow gap distances between the electrodes. The yielding behavior under no external electric fields was also discussed. The wall slip at the interface between the parallel plates and the nano-suspension was briefly discussed. Under the dc electric field, a fine chain-like microstructure was optically found within a narrow gap of 50 μm between the electrodes in the quiescent state. The nano-suspension confined to a narrow gap of 65 μm between the parallel plates was rather viscoelastic even at the highest strength of the electric field of 16 kV·mm⁻¹. Furthermore, fast and slow relaxations of the dynamic moduli were found after removal of the electric field. It was pointed out that the linear viscoelasticity was an appropriate measure of the microstructure before yielding.     

La_2Ti_6O_(15)-CeTi_(21)O_(38)-PbTiO_3 ceramics formed in gaseous penetration of La-Ce into PbTiO_3 and their electric properties

PbTiO3 ceramics, which are typical ferroelectric materials, are useful in various applied fields. For example, it has a very good candidacy for piezoelectric materials for high temperature and high sensibility. In recent years, the studies on doped PbTiO3 ceramics have received consid-erable attention[1—3]. The modified PbTiO3 ceramics doped with Ca2+, Sm3+, Y3+, Ce4+ etc. have some better properties: their Curies temperature decreases, their tetragonal distortion degree de-grades and th…     

Catalysis Conversion Methane into C2 Hydrocarbons via Electric Field Enhanced Plasma

In this paper the effect of catalyst and carrier in electric field enhanced plasma on methane conversion into C2 hydrocarbons was investigated. Methane coupling reaction was studied in the system of continuous flow reactor on Ni, MoO3, MnO2 catalysts and different ZSM-5 carriers. The per pass conversion of methane can be as high as 22%, the selectivity of ethylene can be as high as 23.8%, of acetylene 60.8%, of ethane 5.4% and of total C2 hydrocarbons was more than 90%. ZSM-5-25 was the better carrier and MnO2 was the better active component. The efficiency of energy was as high as 7.81%.     

La1—xMxFeyCo1—yO3型复合氧化物（M=Sr,Ba）的合成,结构及电性能

钙钛矿型的稀土与过渡金属复合氧化物(ABO_3)及部分稀土为碱土金属置换的A_(1-x)M_xBO_3型复合物在最近20年来研究较多,并在催化气敏,超导等方面取得了良好进展。但对A_(1-x)M_xB_(1-y)N_yO_3型复合物却研究甚少。本文合成了一系列的La_(1-x)M_xFe_yCo_(1-y)O_3(M=Sr或Ba)钙钛矿型复合氧化物,研究了它们组成与电性的变化规律。     

Charge reversal at the air/water interface as inferred from the thickness of foam films

Experiments are reported with foam films from aqueous solutions with increasing concentration of a cationic surfactant. A correlation is established between the foam film thickness and the possible variation of diffuse electric layer potential at the air/water interface from a negative value in absence of surfactant to positive values at higher surfactant concentrations. It is concluded that a charge reversal at the air/water interface is expected to occur under increasing concentration of cationic surfactants in aqueous solutions.     

Investigation of Quantitative Relationship between Adsorbed Amount of Solute and Solvent Concentration at Relatively High Solute Concentration by Frontal Analysis in RPLC

IntroductionManyfactors ,includingTraube’srule ,temperature ,solubilityofsolute ,inorganicsalt,thestructureofadsor bentandthenatureandconcentrationofthesolvent,affectsoluteadsorptioninaliquid solidsystem .1Amongthemsolventeffectsareofsignificance .Dispersionsofsilicaarestabilizedbyethanol.Itisreportedthatsolventfilmthick nessisgreatestinmixturesof 5 0percentethanolwithwa ter.2 TherepulsionbetweendispersedparticlesisabovetheeffectsfromthedoublelayerandvanderWaalsforces3andisattributedtostruc…     

电场辐照前后某些中药有效成分的质谱分析

利用快原子轰击质谱（ＦＡＢＭＳ）及解吸电子轰击质谱（ＤＥＩＭＳ）方法，分析了电场辐照前后的５种中药有效成分，证明电场辐照灭菌并不改变其化学结构，讨论了底物效应及正，负快原子轰击质谱的差异，以及与电吸电子轰击质谱的不同断裂规律，同时利用Ｂ／Ｅ联动扫描（亚稳离子测定）进行了验证。