Polarization of systems with complex geometry

The article analyzes the current state of studies of concentration polarization in the systems containing various combinations of ion-exchange particles, fibers, membranes and charged diaphragms. It is shown that polarization characteristics of such systems depend not only on the properties of each of the polarized objects and the potential difference applied to the system, but also on the positioning of the system elements in relation to each other.     

Microwave dielectric spectra and molecular relaxation in formamide-N,N-dimethylformamide binary mixtures

The dielectric dispersion and absorption spectra of formamide (FA), N,N-dimethylformamide (DMF) and their binary mixtures are investigated in the frequency range of 500 MHz to 20 GHz at 30 °C in view of the organic synthesis by microwaves heating using amides solvents. The concentration dependent values of molecular reorientation relaxation times lower than that of the ideal mixing behaviour have been attributed to the cooperative dynamics of H-bonded FA–DMF structures. The molar ratio of stable adduct is 2:1 of FA to the DMF, which is determined from the concentration dependent excess static dielectric constant and the relaxation time plots of these binary mixtures. Electrode polarization effect and ionic conduction in FA and DMF were investigated from their dielectric dispersion spectra in the low frequency region of 20 Hz to 1 MHz.     

Temperature-dependent dielectric relaxation study of binary mixture using the time domain reflectometry method

Dielectric relaxation study of N,N-dimethylformamide (DMF) has been carried out with butylene glycol (BLG, i.e. 1,4-butanediol) at different temperatures. Time domain reflectometry in reflection mode has been used to measure the reflection coefficient in the frequency range from 10?MHz to 20?GHz. The dielectric parameters, static dielectric permittivity (ε ₀) and relaxation time (τ), have been obtained by Fourier transform and least squares fit methods. The experimental results show non-linear variation in dielectric permittivity, and relaxation time with volume fraction of BLG confirms the structural formation due to the intermolecular interaction between DMF and BLG. The variations in excess permittivity (ε^E ), excess inverse relaxation times (1/τ) ^E and Kirkwood correlation factors (g ^eff?;g?^f ) for the binary mixtures have also been reported in this article.     

Intermediate nematic phases in binary systems with complex formation

The phase diagrams of some binary systems of smectogenic compounds are presented in which intermediate nematic phases occur over a large concentration range. An attempt has been made to interpret this behaviour in terms of structural differences between the smectic A phases of the components.     

Finite-element calculations for dielectric relaxation of one-sphere systems in a parallel-electrode measuring cell

Using the finite-element method (FEM), the frequency dependence of conductivity and relative permittivity was calculated for a heterogeneous specimen in which a sphere was placed in a medium. The FEM calculations were made for the whole system in which the specimen was located in a measuring cell comprising two parallel electrodes and a spacer with a cylindrical sample cavity, as in practical measurements. Values of the conductivity and the permittivity of the sphere and the medium were chosen so as to simulate specimens of water-in-nitrobenzene (W/N) and oil-in-water (O/W) types. When the volume ratio of the sphere to the sample cavity p was below 0.1, the frequency dependence of conductivity and permittivity was in good agreement with that described by Wagner's theory for both the W/N and O/W specimens. When p was greater than 0.1, deviations from Wagner's theory were found for limiting values of the conductivity and permittivity at low and high frequencies for both the W/N and O/W specimens, and for the relaxation time for the W/N specimens. Received: 15 July 1998 Accepted in revised form: 5 November 1998     

Diagrams for complete representation of binary mononuclear complex systems

Solution equilibria are calculated from the system of equations expressing the mass balance and the law of mass action. The solution of these equations usually requires the use of complicated iterative procedures. It is shown in the present paper, that for mononuclear complex formation, the whole system can be represented by a single diagram exhibiting all of the important chemical information, including solubility equilibria. The data necessary for the construction of the diagrams can be calculated directly without iterative procedures.     

Non-markovian effects in dielectric relaxation

A generalized Nee—Zwanzig equation is proposed to describe both low and high frequency dielectric relaxation. It is shown that the inertial effect is closely related to the non-markovian character of the differential equation governing the time evolution of the dipole—dipole autocorrelation function. Comparison with experimental results is given.     

Defect-diffusion models of dielectric relaxation

Dielectric relaxation due to defect-diffusion in liquids, as introduced by Glarum, is considered for the case that reorientation of a molecule at time t ? 0 may be due not only to the nearest defect at t = 0, but to any defect in the liquid. For one-dimensional diffusion one then obtains the empirical relaxation function introduced by Williams and Watts with β = 0.5, and for three-dimensional diffusion a result only slightly differing from that for a single relaxation time. It is concluded that a model of dielectric relaxation by diffusion of defects only leads to considerable deviations from a single relaxation time when the diffusion is restricted in some way.     

Efficient moves for global geometry optimization methods and their application to binary systems

We show that molecular dynamics based moves in the minima hopping method are more efficient than saddle point crossing moves. For binary systems we incorporate identity exchange moves in a way that allows one to avoid the generation of high energy configurations. Using this modified minima hopping method, we re-examine the binary Lennard-Jones benchmark system with up to 100 atoms and we find a large number of new putative global minima.     

Effect of steric hindrance of ketones in the dielectric relaxation of methanol+ketone systems

The reorientation activation energies of five methanol?+?ketone systems were determined from the study of the variation of dielectric permittivity with temperature between 303 to 333?K at X band frequency. The results of the activation parameters are interpreted in terms of the rotation of the molecules about the C–O–H hydrogen bond, using a previously reported conformation obtained from semi-empirical and ab initio calculations as the basic conformer. The ketones studied are acetone, 2 butanone, 3 pentanone, cyclohexanone and acetophenone.     

Coexistence of magnetization relaxation and dielectric relaxation in a single-chain magnet

A novel single-chain magnet, [MnIII3O(Meppz)3(EtOH)4(OAc)] (1), has been successfully synthesized from a secondary building block [MnIII3O(Meppz)3(EtOH)5Cl] (2) with an S = 1 ground state. SCM 1 exhibits both magnetization relaxation and dielectric relaxation properties.     

Microwave dielectric relaxation in some hydrogen-bonded solutions

Dielectric constant and loss values have been obtained between 1 and 35 GHz for several:polyhydroxyl alcohols in p-dioxane solution at 25°C. The data have been analyzed in terms of a Cole-Cole distribution. The relaxation times are sensitive to the proximity of the hydroxyl groups and the degree of intramolecular hydrogen bonding.     

Molecular theory of dielectric relaxation in nematic dimers

This paper reports a theory for the dielectric relaxation of dimeric mesogenic molecules in a nematic liquid crystal phase. Liquid crystal dimers consist of two mesogenic groups linked by a flexible chain. Recent experimental studies [D. A. Dunmur, G. R. Luckhurst, M. R. de la Fuente, S. Diez, and M. A. Perez Jubindo, J. Chem. Phys. 115, 8681 (2001)] of the dielectric properties of polar liquid crystal dimers have found unexpected results for both the static (low frequency) and variable frequency dielectric response of these materials. The theory developed in this paper provides a quantitative model with which to understand the observed experimental results. The mean-square dipole moments of alpha,omega-bis[(4-cyanobiphenyl-4'-yl]alkanes in a nematic phase have been calculated using both the rotational isomeric state model and a full torsional potential for the carbon-carbon bonds of the flexible chain. The orienting effect of the nematic phase is taken into account by a parametrized potential of mean torque acting on the mesogenic groups and the segments in the flexible chain. Results of calculations using the full torsional potential are in excellent agreement with experimental results for comparable systems. The probability density p(eq)(beta(A),beta(B)) for the orientation of the mesogenic groups (A,B) along the nematic director is also calculated. The resultant potential of mean torque is a surface characterized by four deep energy wells or sites equivalent to alignment of the terminal groups A and B approximately parallel and antiparallel to the director; of course, the reversal of the director leads to equivalent sites. This potential energy surface provides the basis for a kinetic model of dielectric relaxation in nematic dimers. Solution of the Fokker-Planck equation corresponding to this four-site model gives the time dependence of the site populations, and hence the time-correlation functions for the total dipole moment along the director. In this model the end-over-end rotation of the molecule, corresponding to simultaneous reversal of both mesogenic groups, is excluded because the activation energy is too large. Results are presented for a number of cases, in which a dipole is located on one or both of the mesogenic groups, and additionally where the groups differ in size. For the latter, under particular conditions, the correlation function exhibits a biexponential decay, which corresponds to two low frequency absorptions in the dielectric spectrum. This is exactly what has been observed for nonsymmetric nematic dimers having different groups terminating a flexible chain. Experimental results over a range of temperature for the nonsymmetric dimer alpha-[(4-cyanobiphenyl)-4'-yloxy]-omega-(4-decylanilinebenzylidene-4'-oxy)nonane can be fitted precisely to the theory, which provides new insight into the orientational and conformational dynamics of molecules in ordered liquid crystalline phases.     

Recent development in dielectric relaxation spectroscopy of polymers

An evaluation strategy for dielectric measurements in the frequency and/or time domain is presented which provides complete information about a relaxation mechanism (intensity, position, and shape of the relaxation function) independent of overlapping with neighboring mechanisms. As an example results on poly-(ethyleneterephthalate) are given.     

On the interpretation of dielectric relaxation in nematogens

The dielectric relaxation in the isotropic phase of liquid crystals is described by the rigid ellipsoid diffusion model.     

Quantum theory of dielectric relaxation in polar solids

A novel approach to the impurity dipole relaxation in polar solids is described in which the dipole reorientational sites are formed by an appropriate electron—phonon coupling interaction. The electronic states used for a two-site formulation are defined as ones pertaining to the impurity and/or the associated intrinsic point defect. The theory takes into account the adiabaticity of the electron transfer in addition to the barrier-controlled ionic tunneling. It compares favorably with available experimental relaxation-time data on alkali halides.