Dielectric process of space-charge polarization for an electrolytic cell with blocking electrodes

The dielectric process of space-charge polarization for an electrolytic cell with blocking electrodes is simulated considering bound charges externally supplied to the electrodes. A numerical calculation is performed to determine the distribution of mobile charges under an ac field satisfying Poisson's equation in which the dielectric constant varies with frequency. An exact frequency-dependent curve of the complex dielectric constant is obtained by including the contribution of bound charges induced by the space-charge polarization itself in Poisson's equation at every frequency. The present model of the space-charge polarization enables one to correctly understand the experimental results on the complex dielectric constant of electrolytic cells in low-frequency regions.     

An interlayer model for the complex dielectric constant of composites

The complex dielectric constant of a composite with an interlayer was studied as a function of the volume fractions and the properties of the filler, the interlayer, and the matrix. The theoretical approach is analogous to the calculation of the shear modulus, the bulk modulus, and the termal expansivity of particulate filled polymers using the interlayer model (IM).An analytical expression describing the influence of an interlayer on the generalized dielectric constant of the composite as a function of the volume fraction and interlayer properties is derived.In the case of a composite with non-conductive constituents, the equations for static and oscillatory electric fields are similar. When conductive constituents are present, the complex dielectric constants have to be replaced by the generalized complex dielectric constants.For a composite of non-conductive materials, without interlayer, the obtained relation reduces to the classical Rayleigh equation. In the case of a composite with conductive constituents, also without interlayer, the complete solution of Wagner's theory is found. Special attention has been paid to the case of a water interlayer in a glass-bead filled non-conductive matrix material.     

Complex and charge transfer between TiO2 and pyrroloquinoline quinone

Pyrroloquinoline quinone (PQQ) forms a tridentate complex with coordinatively unsaturated titanium atoms on the surface of approximately 4.5 nm TiO2 particles; an association constant of K = 550 M-1 per Ti(IV)surf has been determined. Low-temperature electron paramagnetic resonance was employed in identification of localized charges and consequently produced radicals and in determination of charge-transfer processes. The photoexcitation of the PQQ-TiO2 complex results in the transfer of conduction band electrons from TiO2 to bound PQQ and the formation of the semiquinone radical. Attaching dopamine (DA) as an electron donor and PQQ as an electron acceptor on the surface of TiO2 results in spatial separation of photogenerated charges; the holes localize on dopamine and electrons on PQQ, with higher yields than for each component separately. In this triad-type assembly (PQQ-TiO2/DA) the PQQ that is bound to the particles acts as a sink for electrons allowing their almost complete scavenging even at temperature as low as 4 K.     

Dielectric relaxation study of aqueous α-amylase using time domain reflectometry technique

Time domain reflectometry technique has been used to study the complex permittivity spectra of aqueous α-amylase solution at different pH. Static dielectric constant and relaxation time were obtained from the complex permittivity spectra using nonlinear least square fit method. The dielectric relaxation parameter increases with an increase in molar concentration of α-amylase in water due to the formation of hydrogen bonding. The hydration numbers were also determined from the static dielectric constant.     

Free energy of charge transfer and intraprotein electric field: method of calculation depends on the charge state of protein at a given structure.

Free energy of charge transfer presents a basic characteristic of reactions such as protonation, oxido-reduction and similar. Evaluation of this quantity requires calculation of charging energy. Proteins are structured dielectrics, and a consistent incorporation of their structure into calculation of intraprotein electric field results in expression for charging energy of an active group in protein, which is essentially different from that for a simple dielectric. An algorithm for semi-continuum calculation of relevant free energies is described. First of the two components of charging energy in protein, energy of the medium response to charge redistribution in reactants, should be always calculated as the charging energy by the charge redistribution using the static dielectric constant of protein. The second term is interaction energy of the charge redistribution with the 'frozen' electric field of the system before reaction. Charges of protein groups, at which the protein structure has been determined, are often different from those before reaction of charge transfer, so is the corresponding intraprotein field. The field is expressed through either both the optical and static dielectric constants of protein or only optical one depending on whether the charges of protein groups before reaction and upon structural analysis are the same or not. Proper allowance for difference in charges of reacting groups before reaction and upon structural analysis of protein is thermodynamically necessary and quantitatively important. The expression for activation free energy for charge transfer in proteins is derived in the form presenting explicitly an invariant contribution of protein structure.     

First principles study of dielectric and vibrational properties of pyrochlore hafnates

We present the first principles study of dielectric, and vibrational properties of pyrochlore hafnates, RE₂Hf₂O₇ (RE = La, Nd, Sm, Eu, Gd, Tb) in their cubic structure using density functional theory and density functional perturbation theory, incorporating ultrasoft pseudopotentials and plane waves. The full set of zone centre Raman and infra red frequencies, along with the contribution of all infra red active modes towards dielectric constant and mode effective charges is calculated and discussed. In all the studied hafnates dominant contribution to static dielectric constant is found to come from three infrared active phonons around 125 cm⁻¹, 170 cm⁻¹ and 305 cm⁻¹. In addition, calculated structural properties are in very good agreement with experimental results. Mixed ionic-covalent bonding is found from the analysis of dynamical charges, static charges and density of states.     

Obtaining charge distributions on geometrically generic nanostructures using scanning force microscopy

We develop the self-consistent sum of dipoles (SCSD) theory for the purpose of recovering charge densities present on nanostructures using scanning force microscope (SFM) force-separation experiments. The dielectric probe is discretized into volume elements characterized by their atomic polarizabilities. Magnitudes of the induced dipole in each element are calculated based on discrete charges placed on the surfaces, dipole-dipole interactions, and dielectric and ionic properties of the surrounding medium. We perform two model-model comparisons, one with a macroscopic dielectric sphere and one with a nanocluster of silicon atoms. In both cases, using a single adjustable parameter, our SCSD theory agrees with the accepted theories to better than 99%. Force-separation curves between a silicon nitride probe and the basal plane of highly oriented pyrolytic graphite in nine ionic concentration and pH combinations were fit with a root-mean-square error of 3.6 pN, an improvement over the 12 pN error obtained using the Derjaguin approximation. These results suggest that the SCSD will be useful in modeling SFM force-separation data to obtain spatially varying charge densities on surfaces with complex geometries.     

反渗透膜UTC-70在水溶液中的介电谱及其解析

根据平面层状体系介电弛豫理论研究了反渗透膜UTC-70在各种浓度氯化钠和氯化钾溶液中的介电弛豫行为.利用计算机拟合的方法得到膜/溶液体系的介电参数,并由此计算得到了UTC-70膜相和水溶液相的相参数,获得了反映反渗透膜UTC-70荷电情况的信息及其与电解质溶液浓度的关系,介电解析的结果解释了介电弛豫的产生机制.     

An interlayer model for the complex dielectric constant of composites: An extension to ellipsoidally shaped particles

A theoretical interlayer model (IL) has been developed for the complex dielectric constant of a composite in which the filler particles are enveloped with a layer of interfacial material. The filler particles can be of any ellipsoidal shape. Special cases such as spherical particles, needles, and fabrics are shown to be covered by the model.The analytical formula as derived describes the composite properties as a function of the volume fractions of the filler, the layer and the matrix material, their dielectric properties and the filler particle shape factor.In the case of a two-phase composite the model reduces to the well-known Sillars relation for the complex dielectric constant of composite which contains filler particles of ellipsoidal shape.The effect of an interfacial layer on the static dielectric constant of the composite is discussed using the model. Next, the special case of a conductive interfacial layer in an otherwise non-conductive composite is discussed; it illustrates the effect of interfacially adsorbed water on the electrical properties of composites. Some practical examples are shown.     

Experimental and theoretical study of the influence of a bias electric field on the dielectric properties of the chiral smectic A* phase

The influence of a bias electric field on the temperature and frequency dependence of the soft mode part of the complex dielectric constant of the chiral smectic A* phase has been studied experimentally. It was found that only close to T_S*CS*A does the bias field have any influence on the experimentally determined quantities. Here the relaxation frequency increased with increasing bias field, while the corresponding dielectric strength decreases. We also present a theoretical calculation of the influence of a bias field on the complex dielectric constant of the chiral smectic A* phase which, apart from minor details, is in accordance with the observed behaviour. Finally we discuss how the nature of the electroclinic effect can be correlated with the influence of the bias field on the smectic A* dielectric constant.     

Particle-interface interaction across a nonpolar medium in relation to the production of particle-stabilized emulsions

Quantitative theory of the particle-interface interaction across a nonpolar medium is developed. We consider a spherical dielectric particle (phase 1), which is immersed in a nonpolar medium (phase 2), near its boundary with a third dielectric medium (phase 3). The interaction originates from electric charges at the particle surface (e.g., the surface of a silica particle immersed in oil). The theoretical problem is solved exactly, in terms of Legendre polynomials, for arbitrary values of the dielectric constants of the three phases. As a result, expressions for calculating the interaction force and energy are derived. These expressions generalize the known theory of the electrostatic image force (acing on point charges) to the case of particles that have finite size and uniform surface charge density. For typical parameter values (silica or glass particles immersed in tetradecane), the image-force interaction becomes significant for particles of radius R > 30 nm. At fixed relative particle-to-interface distance, the force increases with the cube of the particle radius. In general, this is a strong and long-range interaction. For micrometer-sized particles, the interaction energy could be on the order of 10(5) k(B)T at close contact, and, in addition, the interaction range could be about 10(5) particle radii. The sign of the interaction depends on the difference between the dielectric constants of phases 2 and 3. When phase 3 has a smaller dielectric constant (e.g., air), the interface repels the particle. In contrast, when phase 3 has a greater dielectric constant (e.g., water), the interaction is attractive. Especially, water drops attract charged hydrophobic particles dispersed in the oily phase, and thus favor the formation of reverse particle-stabilized (Pickering) emulsions. The particle-interface interaction across the oily phase is insensitive to the concentration of electrolyte in the third, aqueous phase.     

The influence of discrete surface charges on the force between charged surfaces

The force between two parallel charged flat surfaces, with discrete surface charges, has been calculated with Monte Carlo simulations for different values of the electrostatic coupling. For low electrostatic coupling (small counterion valence, small surface charge, high dielectric constant, and high temperature) the total force is dominated by the entropic contribution and can be described by mean field theory, independent of the character of the surface charges. For moderate electrostatic coupling, counterion correlation effects lead to a smaller repulsion than predicted by mean field theory. This correlation effect is strengthened by discrete surface charges and the repulsive force is further reduced. For large electrostatic coupling the total force for smeared out surface charges is known to be attractive due to counterion correlations. If discrete surface charges are considered the attractive force is weakened and can even be turned into a repulsive force. This is due to the counterions being strongly correlated to the discrete surface charges forming effective, oppositely directed, dipoles on the two walls.     

Theory of the effect of small ions on the electrical admittance of macroion solutions

A general theory is given on the electrical admittance of a parallel plate capacitor filled with a conductive medium containing charged particles by considering both their electric atmospheres and the electric field due to charges induced on the electrodes. The theory is applied to a dilute macroion solution with added salt and it is found that the low frequency dielectric response of the solution reflects the motions of the macroion and bound small ions and the effect of motion of the ion atmosphere around the macroion is canceled out by the current due to the induced charges on the electrodes.     

Characterization and structural study of the complex of Al(III) with 2,4-dihydroxy-benzophenone. Ionic strength and solvent effects

The complexation reaction between AlCl(3) and 2,4-dihydroxy-benzophenone with varying permittivity and ionic strength of the reaction medium was investigated by theoretical and experimental procedures, namely, density functional (DFT) and UV-vis spectroscopic methods, respectively. The stoichiometric composition of the complex formed, which was determined by means of the molar ratio method, is 1:1. The molar absorptivity and stability constant of the complex were determined using a method designed by the authors. It was observed that the stoichiometric composition of the complex does not change with the used solvents and that the stability constant in methanol is higher than ethanol. Kinetic experiments in solutions with different ionic strength were also performed. The results obtained permit to conclude that the complex is formed through of a mechanism whose rate-determining step is a reaction between two ions with opposite unitary charges. In the theoretical study performed at the B3LYP/6-31G(d) level of theory using Tomasi's model, it was proposed that the formation of the complex involves one simple covalent bond between the aluminum atom and the oxygen atom of o-hydroxyl group of the ligand and a stronger coulombic attraction (or a second covalent bond) between the central atom and the carbonyl oxygen atom of 2,4-dihydroxy-benzophenone. Using the calculated magnitudes, it was predicted that the complex formed has higher thermodynamic stability in methanol than ethanol. It was also concluded that the planarity of the chelate ring favors a greater planarity of 4-hydroxy-benzoyl group of the complex with respect to the ligand, which agrees with the observed batochromic shifts. The formulated theoretical conclusions satisfactorily match the experimental determinations performed.     

Free energy evaluation of the p53-Mdm2 complex from unbinding work measured by dynamic force spectroscopy

The complex between the tumor suppressor p53 and its down-regulator Mdm2 has been studied by dynamic force spectroscopy and the unbinding data have been analyzed in the framework of the Jarzynski theoretical approach. Accordingly, the unbinding equilibrium free energy has been determined from the work done along several non-equilibrium paths from the bound to the unbound state in the single molecule regime. An unbinding free energy of -8.4 kcal mol(-1) has been found for the complex; such a value is in a good agreement with that measured both in the bulk by isothermal titration calorimetry and that obtained from theoretical computing at the single molecule level. The determination of the unbinding free energy, together with the knowledge of the dissociation rate constant and energy barrier width, as previously obtained by dynamic force spectroscopy, adds rewarding insights on the energy landscape for this complex which is currently at the focus of anticancer drug design.     

Ionic electrets: electrostatic charging of surfaces by transferring mobile ions upon contact

This paper describes the fabrication and characterization of ionic electrets-materials that bear a long-lived electrostatic charge because of an imbalance between the number of cationic and anionic charges in the material. Crosslinked polystyrene microspheres that contain covalently bound ions and mobile counterions transfer some of their mobile ions in air, in the absence of bulk liquid, to another material upon contact. According to the ion-transfer model of contact electrification, this selective transfer of mobile ions yields microspheres that have a net electrostatic charge. A tool that operates on the principle of electrostatic induction measures the charge on individual microspheres (50-450 microm in diameter). Microspheres with a variety of covalently bound ionic functional groups (tetraalkylammonium, alkyltriphenylphosphonium, alkylsulfonate, and arylsulfonate) acquire charges consistent with this ion-transfer mechanism. The charge on a microsphere is proportional to its surface area (ca. 1 elementary charge per 2000 nm2) and close to the theoretical limit imposed by the dielectric breakdown of air. The charge density in an atmosphere of SF6 is more than twice that in an atmosphere of N2. These observations suggest that the charge density of these ionic electret microspheres is limited by the dielectric breakdown of the surrounding gas. Functionalizing the surfaces of glass or silicon with covalently bound ions and mobile counterions generates ionic electrets from these inorganic substrates. Soft lithography can pattern charge on a planar silicon surface (with oxide) and on the surface of 250-mum glass microspheres.     

Modeling the surface charge evolution of spherical nanoparticles by considering dielectric discontinuity effects at the solid/electrolyte solution interface

It is well known that the electrostatic repulsions between charges on neighboring sites decrease the effective charge at the surface of a charged nanoparticle (NP). However, the situation is more complex close to a dielectric discontinuity, since charged sites are interacting not only with their neighbors but also with their own image charges and the image charges of all neighbors. Titrating site positions, solution ionic concentration, dielectric discontinuity effects, and surface charge variations with pH are investigated here using a grand canonical Monte Carlo method. A Tanford and Kirkwood approach is used to calculate the interaction potentials between the discrete charged sites. Homogeneous, heterogeneous, and patch site distributions are considered to reproduce the various titrating site distributions at the solid/solution interface of spherical NPs. By considering Coulomb, salt, and image charges effects, results show that for different ionic concentrations, modifications of the dielectric constant of NPs having homogeneous and heterogeneous site distributions have little effect on their charging process. Thus, the reaction field, due to the presence of image charges, fully counterbalances the Coulomb interactions. This is not the case for patch distributions, where Coulomb interactions are not completely counterbalanced by the reaction field. Application of the present model to pyrogenic silica is also performed and comparison is made with published experimental data of titration curves at various ionic concentrations.     

Molecular pair potential of chiral amino acid amphiphile in Langmuir monolayers on the basis of an atomistic model

In the present work, the pair potential of enantiomeric N-palmitoyl aspartic acid amphiphile monolayer at the air/water interface is calculated based on an atomistic model. The molecular structure and partial charges are calculated using two semi empirical (PM3, AM1) and one empirical (Gasteiger and Marcili) methods. A distance-dependent dielectric function is used to represent the interfacial dielectric constant at the aqueous subphase. The present study indicates that a pair of molecules have favorable interaction at specific ranges of mutual orientations. Other orientations are favorable but at larger separations. Favorable electrostatic interaction at a specific combination of orientation and short separations of the head groups significantly contribute to the total energy. The curvature of the domain boundary is suggested to be driven by the favorable arrangement which is dependent on the pair potential of molecules. The use of charges obtained by the PM3 and GM do not lead to a significant variation of the orientation-dependent features, while the AM1 predicts higher partial charges and interactions are stronger than the former two methods. However, orientation-dependent features remain the same. The variations in the LJ parameters and charges indicate that the conclusions made are insensitive to the choice of parameters. The mutual favorable interaction predicted by calculation agree with the handedness of curvature of domains.     

Intramolecular scrambling processes of the complex of cadmium(II) and ethylenediaminetetraacetic acid in water-dioxan mixtures; an n.m.r. investigation

Summary The kinetics of the inversion of configuration of the nitrogen atoms in the complex formed from ethylenediaminetetraacetic acid (EDTA) and cadmium(II) has been investigated by n.m.r. in water-dioxan mixed solvents containing up to 20% (mole/mole) of organic component. A DNMR computer program has been used to calculate theoretical spectra and determine the rate constant of the process in solvents of different compositions. The rate of nitrogen inversion appears to increase with the amount of dioxan present in the solvent in spite of the diminution in dielectric constant, which should make the coordination links more inert. This results suggests that solvent displacement must play a predominant role in the mechanism of exchange.