DFT study on the influence of electric field on surface‐enhanced Raman scattering from pyridine–metal complex

The influence of a static external electric field on surface‐enhanced Raman scattering is investigated by calculating the Raman spectra and excited state properties of pyridine–Au₂₀ complex with the density functional theory and time‐dependent density functional theory method. The external electric field with orientation parallel (positive) or antiparallel (negative) to the permanent dipole moment is respectively applied on the complex. This field slightly changes the equilibrium geometry and polarizabilities, which results in shifted vibration frequencies and selectively enhanced Raman intensities. The changes of charge transfer (CT) excited states in response to the electric field are visualized by employing the charge difference densities. Further, the energy of charge transfer transition is tuned by electric field to be resonant or not with the incident light, leading to the Raman intensities are enhanced or not enhanced. At the same time, the intensities of vibration modes are sensitive to the orientation of the field. The positive electric field enhances the totally symmetric ring breathing mode (~1009 cm⁻¹) but suppresses the trigonal ring breathing mode (~1051 cm⁻¹). On the contrary, the mode at 1051 cm⁻¹ is more enhanced than the mode at 1009 cm⁻¹ when the negative electric field is applied on the complex. The Raman spectra could be modulated by tuning the strength and direction of the electric field. Copyright © 2013 John Wiley & Sons, Ltd.     

Adsorption of polyelectrolytes at an oppositely charged surface

We develop a scaling theory of polyelectrolyte adsorption at an oppositely charged surface. At low surface charge densities, the thickness of the adsorbed layer is determined by the balance between electrostatic attraction to the charged surface and chain entropy. At high surface charge densities, it is determined by the balance between electrostatic attraction and short-range monomer-monomer repulsion. These different stabilizing mechanisms result in the nonmonotonic dependence of the layer thickness on the surface charge density.     

混合电解质溶液中考虑介电饱和度的表面电位评估原理

基于非线性泊松-玻尔兹曼方程，推导了混合电解质溶液中考虑介电饱和度的表面电位的解析表达式. 近似解析解和精确数值解计算出的表面电位在很大范围的电荷密度和离子强度条件下均具有很好的一致性. 当表面电荷密度大于0.30 C/m^{2 时，介电饱和度对表面电位的影响变得尤为重要；当表面电荷密度小于0.30 C/m2时，可忽略介电饱和度的影响，即基于经典泊松-玻尔兹曼方程可获得有效的表面电位解析模型. 因此，0.3 C/m2可作为是否考虑介电饱和度的颗粒临界表面电荷密度值. 在低表面电荷密度时，考虑介质饱和度的表面电位解析模型可自然回归到经典泊松-玻尔兹曼理论的结果，得到的表面电位可以正确地预测一价和二价反离子之间的吸附选择性.}     

Electrophoretic mobility of model colloids and overcharging: theory and experiment

Several theories claim that ion-ion correlations play an important role in the electric double layer of colloids. One of the most outstanding predictions is overcharging, which would take place at high electrolyte concentrations and surface charge densities. The counterion concentration next to the surface can become so large that the particle charge is overcompensated and the overcharging occurs. Sometimes this would also involve a reversal of the ζ potential, but this phenomenon has been observed rarely through mobility measurements. This study explores the matter further. The electrophoretic mobility is measured for latex particles with moderate and extremely large surface charge densities at high ionic strengths (up to 2 M) in solutions of symmetric electrolytes. The results are analysed within the so-called hypernetted chain/mean-spherical approximation (HNC/MSA) and a Poisson-Boltzmann approach. In this way, the relevance of ion-ion correlations in practice and the occurrence of overcharging are probed experimentally.     

Theoretical study on SERRS of rhodamine 6G adsorbed on Ag2 cluster: chemical mechanism via intermolecular or intramolecular charge transfer

The problem of the chemical enhancement of rhodamine 6G (R6G) adsorbed on silver cluster has been theoretically investigated by charge difference densities (CDDs) to show the direct charge transfer (CT) evidence. For surface‐enhanced resonance Raman scattering (SERRS) of R6G excited at 514.5 nm, the enhancements of v(151) and v(154) result from weak intermolecular (from Ag to R6G) CT and the strong intramolecular CT [similar to that of resonance Raman scattering (RRS) of R6G], respectively. The possibility of the SERRS of R6G contributed from pure intermolecular CT is also discussed, when the incident light is close to the new metal–R6G CT excited state at 1571.4 nm. Meanwhile compared with the absorption process the fluorescence yield of R6G is investigated by transition densities and CCDs. Copyright © 2008 John Wiley & Sons, Ltd.     

Development of the dimple instability on liquid 4He

Electrons on the surface of liquid ⁴He have been used to study the transition from a homogeneous two-dimensional charge distribution to the modulated charge density regime where the so-called dimple crystal is formed. The observation of hysteresis effects suggests that the transition is discontinuous.     

Charge transition densities for the excitation and nucleon decay of the giant dipole resonance in16O

Predictions on charge transition densities in¹⁶O for the excitation of the giant dipole resonance are given within a continuum self-consistent RPA-SK3 theory. The nuclear states are allowed to decay with proton or neutron ejection. The discussion is focused on the analysis of the radial behaviour of transition densities in terms of their microscopic structure. The rôle of RPA ground state correlations is clarified. The surface properties of resonant nuclear states extracted from photonuclear and (e, e′ x) reactions at low momentum transfer are confronted with the full radial dependence of the resonant structure shown in charge transition densities.     

Triboelectrification of pharmaceutically relevant powders during low-shear tumble blending

A test apparatus and methods used to study the influence of physical properties of pharmaceutically relevant powders and powder mixtures on triboelectric behavior during low-shear blending is described. Samples were mixed using a stainless steel blender and dispensed directly into a Faraday pail to measure charge. Eight different materials commonly used in pharmaceutical solid dosage formulation were characterized. Particle size and known concentrations of discrete particle size distributions were shown to influence the measured surface charge densities consistent with previously reported results. Further, binary mixtures of the model compounds were studied and found to produce unanticipated trends in surface charge density. The effectiveness of process parameters, including hold time after processing, and formulation design in controlling the surface charge density in particulate systems is also discussed with supporting results obtained from the proposed apparatus.     

Interactions of surface states of copper with transition metals and cesium

The pseudopotential augmented-plane-wave method was used to study the surface structure of thin copper films with monolayers of Co, Ni, and Cs. Local densities of electron states, distributions of charge densities in the layers, and electron energy spectra are analyzed. The effect of adsorbates on the electronic properties of the Cu(001) surface and work function are discussed. Satisfactory agreement with available experimental data has been obtained.     

基于AFM的固液界面表面电荷密度测量方法

固液界面的表面电荷会影响微纳流体系统的流体阻力,因此如何测量固液界面的表面电荷密度以及分析表面电荷的产生机理对于研究表面电荷对流体阻力的影响具有较大的意义。提出了一种基于接触式AFM的固液界面表面电荷密度测量方法。基于该方法测量了浸在去离子水和0.01 mol/L的NaCl溶液中的高硼硅玻璃和二氧化硅样本的表面电荷密度,并研究了溶液pH值对表面电荷的影响。研究结果表明高硼硅玻璃和二氧化硅由于表面硅烷基的电离带负电。溶液pH值和离子浓度的增加都会增加浸在去离子水和0.01 mol/L的NaCl溶液中高硼硅玻璃和二氧化硅的表面电荷密度的绝对值。     

Numerical computer calculation of distribution of similar point charges at the dielectric surface

Results of numerical calculation of the distribution of similar point charges over a uniformly charged dielectric plane are presented for different surface charge densities and surface temperatures. It is shown that, in the case of the surface charge density ranging from 2 × 10⁻⁶ to 7 × 10⁻⁵ C/m² and temperatures ranging from 300 to 800 K, the Lindemann criterion is fulfilled for the average deviation of the point charge from the equilibrium position, and the collection of point charges at the dielectric surface can be regarded as a 2D Coulomb crystal.     

Generation of spin current by Coulomb drag

Coulomb drag between two quantum wires is exponentially sensitive to the mismatch of their electronic densities. The application of a magnetic field can compensate this mismatch for electrons of opposite spin directions in different wires. The resulting enhanced momentum transfer leads to the conversion of the charge current in the active wire to the spin current in the passive wire.     

Giant Raman scattering by pyridine and CN− adsorbed on silver

The giant RS by pyridine and CN^? on Ag is accompanied by a strong RS continuum which is attributed to inelastic light scattering by charge carrier-excitations. The enhanced RS by the adsorbed molecules and by the charge carrier-excitations are attributed to surface roughness enhanced EM fields at the metal surface resulting from the excitation of transverse collective electron-excitations and surface-EM modes, and to surface roughness-induced radiative-excitation and radiative-recombination of particle-hole pairs.     

Nonlinear periodic waves on the charged surface of a deep low-viscosity conducting liquid

An analytical expression for the profile of a finite-amplitude wave on the free charged surface of a deep low-viscosity conducting liquid is derived in an approximation quadratic in wave amplitude-to-wavelength ratio. It is shown that viscosity causes the wave amplitude to decay with time and makes the wave profile asymmetric at surface charge densities subcritical in terms of Tonks-Frenkel instability. At supercritical values of the surface charge density, taking account of viscosity decreases the growth rate of emissive protrusions on the unstable free surface, slightly broadens them for short waves, and narrows for long ones. Analytical expressions for the wave frequencies, damping rates, and instability growth rates with regard to viscosity are found.     

Shape change of nanocontainers via a reversible ionic buckling

We demonstrate that small charged nanocages can undergo reversible changes of shapes by modifying the ionic conditions including salt concentration, pH, and dielectric permittivity of the medium. Using numerical simulations, we analyze structures with various charge stoichiometric ratios. At zero or low charge densities, the shape of the cage is determined by its elastic properties, and the surface charge pattern is dictated by the globally fixed geometry. As the charge density per molecule increases, the shape is strongly affected by the electrostatic forces. In this regime, the shape of the nanocage is controlled by the charge distribution.     

Surfaces with quenched and annealed disordered charge distributions

We consider surfaces with disordered charge distribution. The disorder can be caused by mobile charges, as for example in mixed lipid bilayers, or by weakly charged surfaces where charge regulation takes place (e.g. carboxyl groups). Using Monte-Carlo simulation methods we find for quenched as well as annealed disordered charge distributions counterion densities close to the surface that are significantly larger than for ordered regularly spaced surface ions. Our field-theoretic results agree well with results obtained from Monte-Carlo simulations of the system. Furthermore, we obtain expressions for the effective interaction between charged colloids and charged rods close to a charged surface and discuss the effect of the surface-ion mobility and polarization charges on the interaction. In general, polarization effects as well as surface-ion mobility lead to a weakening of the effective interaction between charged objects.     

One-Dimensional Fluid Model for Dust Particles in Dual-Frequency Capacitively Coupled Silane Discharges

A self-consistent fluid model, which incorporates density and flux balances of electrons, ions, neutrals and nanoparticles, electron energy balance, and Poisson＇s equation, is employed to investigate the capacitively coupled silane discharge modulated by dual-frequency electric sources. In this discharge process, nanoparticles are formed by a successive chemical reactions of anion with silane. The density distributions of the precursors in the dust particle formation are put forward, and the charging, transport and growth of nanoparticles are simulated. In this work, we focus our main attention on the influences of the high-frequency and low-frequency voltage on nanoparticle densities, nanoparticle charge distributions in both the bulk plasma and sheath region.     

The converse magnetoelectric coupling in asymmetric granule/matrix composite film with Ni/PZT component

In this work, a type of asymmetric granule/matrix composite film is designed, where the Ni granule is dispersed in PZT matrix, meanwhile the top and bottom electrode is constituted by Au and SRO respectively. Predicted through the electrostatic screening model and mean field approximation, considerable electrostatic charge is induced on Ni granule surface by ferroelectric PZT polarization. Predicted through the spin splitting model and spherical shell approximation, both the magnetization and magnetic anisotropy of Ni granule are modulated by ferroelectric PZT polarization. As the volume fraction of Ni granule is increased, the electric modulation of magnetization and magnetic anisotropy is reduced and enhanced respectively. As the dimension of granule/matrix composite is varied, such modulation is retained. Due to the large area–volume ratio of nano-granule, this work benefits to realize the converse magnetoelectric coupling in nanoscale.     

亚乙基硫脲分子激发拉曼虚态的研究

本文从拉曼峰强入手,求得了亚乙基硫脲(ETU)分子的"时间分辨键极化率",并讨论了该分子的激发拉曼虚态性质,发现了该分子"激发虚态电子向分子外围键流动"、"电子弛豫后的键极化率分布与基态电子的密度分布相似"、"不同激发波长下的键极化率衰减时间满足不确定关系"等特点。本文还研究了该分子的表面增强拉曼光谱,指出"电荷转移机制"的极化率弛豫时间长于"电磁增强机制"等与表面增强拉曼效应相关的结论。