Numerical calculation of the dielectric relaxation time distribution function in polar liquids

A numerical method for calculation of the relaxation time distribution function based on the discrete Fourier transform of the dispersion part of the complex dielectric permittivity is developed. The time relaxation distribution function is found for water; its dispersion of relaxation times is narrow. This is explained by the presence of distorted hydrogen bonds (the Pople model).Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 3, pp. 37–40, March, 1982.     

Computer simulation of ionic systems. Influence of boundary conditions

The results of molecular dynamics calculations for systems of charged particles under periodic boundary conditions are reported for the case in which the periodic array of particles makes a macroscopically large sphere surrounded by a continuum of dielectric constant ?′. It is shown that thermodynamic and most dynamic properties are independent of the nature of the surrounding medium. The conductivity σ(ω) of the system depends strongly on the dielectric properties of the surrounding medium.     

Plasmon modes at a wedge using a non-local dielectric function

Plasmon modes at a wedge have been obtained by using a non-local dielectric function. It is shown that the effect of this dielectric function is roughly equivalent to rounding the edge of the wedge but using a local dielectric function.     

Calculation of the dielectric function for highly excited polar semiconductors

The optical dielectric function of an electron-hole plasma in highly excited polar semiconductors with a direct band gap is calculated by solving a Bethe-Salpeter equation for the polarization function. The screening of the Coulomb potential is treated in a damped phonon-plasmon-pole approximation. We include the complex dynamical self-energy corrections as well as electron-hole correlations.Project of the Sonderforschungsbereich Frankfurt/Darmstadt, financed by special funds of the Deutsche Forschungsgemeinschaft     

Quasiclassical boundary conditions for Fermi liquids at surfaces

The general boundary conditions at surfaces are derived within the quasiclassical theory of superfluidity in Fermi liquids (superconductors, superfluid³He). These conditions supplement the transport-like equations first introduced into the theory of superconductivity by G. Eilenberger, and allow a quantitative analysis of superfluids near a wall.     

Formation of associates of solvated cations in salt solutions in polar dielectric liquids

Experimental results are presented on excitation of oscillations of polarization charges of solvated ions in an aqueous solution of a mixture of cerium and lead nitrates under an external asymmetric electric field and the directed motion of solvated cerium and lead cations, caused by this process. The applicability of the approximation of the existence of a self-consistent electric field in the solution volume to explain the observed frequency ranges of the manifestation of the effect of electroinduced selective drift of solvated cations is demonstrated. The results of a theoretical analysis of the possibility of forming associates from solvated ions are presented.     

Anisotropic dielectric function in polar nanoregions of relaxor ferroelectrics

The Letter suggests treating the infrared reflectivity spectra of single crystal perovskite relaxors as fine-grained ferroelectric ceramics: locally frozen polarization makes the dielectric function strongly anisotropic in the phonon frequency range and the random orientation of the polarization at nanoscopic scale requires taking into account the inhomogeneous depolarization field. Employing a simple effective medium approximation (the Bruggeman symmetrical formula) turns out to be sufficient for reproducing all principal features of room temperature reflectivity of Pb(Mg(1/3)Nb(2/3))O3. One of the reflectivity bands is identified as a geometrical resonance entirely related to the nanoscale polarization inhomogeneity. The approach provides a general guide for systematic determination of the polar mode frequencies split by the inhomogeneous polarization at the nanometer scale.     

Theory of polar liquids

Two recent contributions to the statistical theory of polar fluids, namely the perturbation theory of Stell, Rasaiah and Narang (SRN) and the meanspherical-approximation (MSA) results of Wertheim, and of Nienhuis and Deutch, are compared and contrasted for the conceptually simple model of hard spheres, diameter R, with central point dipoles, of strength μ (dipolar hard spheres). It is shown that the MSA approach replaces correlation functions which enter correctly into the SRN theory by their low-density limits : to this extent it is unsatisfactory. On the other hand the MSA work does suggest reasons why the naive Padé approximant featuring in SRN theory may be expected to do reasonable justice to the physics of the problem. Numerical comparisons of the excess free-energy (as compared with non-polar hard spheres) as a function of reduced density, ρ* = ρR ³, are given at two temperatures, T* = 2 and T* = 0·25, where T* = kTR ³/μ². Similar curves, for T* = 1 and T* = 0·5, are available from the authors. The gas-liquid (T*, ρ*)-phase boundary is located, near the critical point, on both theories, as are the vapour pressure curves. These are calculated using the Carnahan-Starling equation of state for hard spheres ; and critical comment is made in justification of employing this in the context of MSA results for the excess quantities. The two theories are found to have appreciably different numerical consequences.     

Quasi-one-dimensional structure of polar liquids

The model of hindered molecular rotation considers a dense polar liquid as an infinite statistical chain of particles bound by dipole forces. The applicability limits of this quasi-one-dimensional model and the nature of possible phase transitions in the system under consideration are discussed.     

Molecular dynamics calculation of the dielectric constant without periodic boundary conditions. I

We outline the difficulties in obtaining a reliable value of the dielectric constant of a fluid using molecular dynamics calculations with periodic boundary conditions, and give some explanation of the observed asymptotic behaviour of h_D (r) and hΔ(r) in Monte Carlo simulations of dipolar hard spheres. An alternative method consisting in simulating a dielectric in vacuum is described. This is applied to two dimensional systems. The pertinent theoretical relations for a dielectric disc in vacuum are therefore derived. It is concluded that relations involving MC or MD computation of <m ²> must be carefully handled.     

Computer simulation of vacancy migration in a fcc tilt boundary

Vacancy jumps in a bicrystal model of Σ = 5 (36.9°) [001] tilt boundary in aluminum have been observed at temperatures between 700 and 800 K by means of molecular dynamics simulation. Preliminary results indicated considerable structure dependence and yielded an activation energy for vacancy migration of 0.38 eV. In contrast to a previous study of vacancy migration in a bcc tilt boundary, thermal activation of a boundary interstitial by Frenkel pair production was not observed.     

A simple capacitive cell for the measurement of liquids dielectric constant under transient thermal conditions

A simple device for the measurement of the complex dielectric permittivity of liquids in various thermodynamic states has been developed. It uses a cylindrical aluminium capacitor of a type currently applied in tuning antenna circuits. The capacitor is filled with the liquid solution under study. A comparison of its capacity is made with that of the nitrogen filled capacitor tested under the same thermal conditions. This comparison allows the determination of the real and imaginary part of the solutions permittivity as a function of temperature (between 150 and 300 K) and frequency (between 100 Hz to 2 MHz). After validating the technique with pure glycerol and pure 1,2-propanediol, spectroscopic measurements have been undertaken on pure and diluted 1,2-propanediol in water. Due to the low heat capacity and the high thermal conductivity of the capacitor, cooling rates of 40 K/min have been achieved inside the solution, allowing measurements in the supercooled liquid and vitreous states. Results are presented and discussed in terms of relaxation and the physical states of the sample. By selecting the required thermal conditions, this device permits the observation of thermal transitions, such as ice crystallisation, and measurements to be conducted in the unstable supercooled liquid state. These measurements are necessary in the development of an effective electromagnetic warming device for vitrified cryoprotective solutions.     

Electromagnetodynamics of polar liquids and suspensions

We study electric and magnetic effects on the dynamics of polar liquids and of fluid suspensions of particles carrying electric and/or magnetic dipole moments. The hydrodynamic equations of motion are discussed in detail and compared with equations proposed in the literature. We derive simplified equations valid on a slow timescale.     

The effect of impedance boundary conditions on the potential function of the boundary diffraction wave theory

A novel potential function of the boundary diffraction wave theory is obtained for the impedance surfaces by the asymptotic reduction of the modified theory of physical integrals. The function is expressed in terms of the direction vectors of the incident and scattered rays. The application of the method is performed on the problem of diffraction of plane waves by an impedance half plane for oblique incidence.     

Pulsed dielectric spectroscopy of supercooled liquids

Pulsed dielectric spectroscopy is introduced as a technique for selectively emphasizing specific components of the non-exponential dielectric response of matter. Samples studied include supercooled liquid propanol, propylene carbonate, and poly(lauryl-methacrylate). It is shown that particular sequences of pulses can be used to emphasize the fast response regime, to produce a cross-over or memory effect, or to eliminate the response of selected components. Furthermore, for materials characterized by broad distributions of relaxation times, the technique facilitates the investigation of a relatively narrow band from that distribution. It is also shown that the time domain spectroscopy can be combined with conventional frequency domain techniques to provide the characterization of dielectric response over an extraordinarily broad spectral range.