Nonlinear ion transport in liquid and solid electrolytes

This paper describes nonlinear ion transport properties of liquid and solid electrolytes. Typically, the relation between ionic current density and electric field becomes nonlinear at electric fields above 50–100?kV/cm. We review the 1st and 2nd Wien effect found in classical strong and weak electrolyte solutions as well as the strong nonlinear ion transport effects observed for inorganic glasses and for polymer electrolytes. Furthermore, we give an overview over models describing nonlinear ion transport in electrolyte solutions, in glasses and in polymers. Recent results are presented for the nonlinear ionic conductivity of supercooled ionic liquids. We show that supercooled ionic liquids exhibit anomalous Wien effects, which are clearly distinct from the classical Wien effects. We also discuss the frequency dependence of higher-order conductivity and permittivity spectra of these liquids.     

Physicochemical properties of ionic liquid mixtures containing choline chloride,chromium (III) chloride and water: effects of temperature and water content

The effects of water addition and temperature on some physicochemical properties of room temperature ionic liquids containing chromium chloride, choline chloride and water in the molar ratio of 1:2.5:x (where x = 6, 9, 12, 15 or 18) have been studied. The density, viscosity, surface tension and conductivity of the liquid mixtures were measured for the temperature range of 25 to 80 °C. Increasing both water content and temperature resulted in decreasing density, surface tension and viscosity and increasing electrical conductivity. The average void radii (hole sizes) for the liquid systems under study were calculated; they were in the range of 1.21 to 1.82 Å. The average hole size was stated to grow with increasing both temperature and water content in the mixture. The variation of the average void radii correlates with the change in viscosity and conductivity. The activation energies of viscous flow and conductivity diminishes with increasing water content in the liquid mixture. There is a strong linear correlation between conductivity and fluidity which indicates that the conductivity of the ionic liquid mixtures is generally controlled by the ionic mobility. A moderate viscosity and higher conductivity of the Cr(III)-containing ionic liquids with extra-water addition (at x > 9) make them suitable for the development of chromium electrodeposition processes.     

Energy landscape of a simple model for strong liquids

We calculate the statistical properties of the energy landscape of a minimal model for strong network-forming liquids. Dynamic and thermodynamic properties of this model can be computed with arbitrary precision even at low temperatures. A degenerate disordered ground state and logarithmic statistics for the local minima energy distribution are the landscape signatures of strong liquid behavior. Differences from fragile liquid properties are attributed to the presence of a discrete energy scale, provided by the particle bonds, and to the intrinsic degeneracy of topologically disordered networks.     

准一维多链无序体系跳跃电导特性

在单电子紧束缚近似下,建立了准一维多链无序体系直流、交流电子跳跃输运模型,通过计算探讨了无序模式、维度效应、温度及外场对其直流、交流电导率的影响.计算结果表明:准一维多链无序体系的直流、交流电导率随着格点能量无序度的增大而减小,非对角无序具有增强体系电子输运能力的作用.随着链数的增加,体系的直流、交流电导率增大,但格点能量无序度较小时,维度效应的影响不明显.在对角无序情况下准一维多链无序体系的交流电导率随温度的升高而增大,而在非对角无序模式下却随温度的升高而减小,但对于直流情况,体系的直流电导率随温度的升     

Low temperature electronic hopping in β-AgI

A frequency dependent conductivity typical of many disordered systems has been observed in the superionic conductor β-AgI at low temperatures. The frequency dependent conductivity is found to be electronic in nature with no evidence for a contribution from ionic hopping. The current results suggest the ionic hopping in superionics is classical in nature with no thermally activated tunnelling.     

Superionic conductors

The so-called superionic conductors represent a class of solid materials showing an unusually high ionic conductivity. Their structure is characterized by strong disorder in the sublattice of conducting ions. We shall describe the dynamic properties of the partially disordered state on the basis of two classes of theoretical models. For stochastic lattice gases we discuss the behavior of various time-correlation functions relevant for inelastic neutron- and light-scattering experiments and for tracer-diffusion measurements. In addition we study a system of interacting Brownian particlés in the presence of a periodic potential as a model for optimized (AgI-type) ionic conductors. A mean-field theory is developed which implies a relationship between the conductivity and structural properties.     

Bosonization for disordered and chaotic systems

Using a supersymmetry formalism, we reduce exactly the problem of electron motion in an external potential to a new supermatrix model valid at all distances. All approximate nonlinear sigma models obtained previously for disordered systems can be derived from our exact model using a coarse-graining procedure. As an example, we consider a model for a smooth disorder and demonstrate that using our approach does not lead to a "mode-locking" problem. As a new application, we consider scattering on strong impurities for which the Born approximation cannot be used. Our method provides a new calculational scheme for disordered and chaotic systems.     

Mobility and conductivity of ionic and bonded defects in hydrogen-bonded chains with nonlinear interactions

The proton conductivity and the mobility arising from motions of the ionic and bonded defects, in hydrogen-bonded molecular systems are investigated by means of the quantum mechanical method. Our two component model goes beyond the usual classical harmonic interaction by inclusion of a quartic interaction potential between the nearest-neighbor protons. Among the rich variety of soliton patterns obtained in this model, we focus our attention to compact kink (kinkon) solutions to calculate analytically, the mobility of the kinkon-antikinkon pair and the specific electrical-conductivity of the protons transfer in the hydrogen-bonded systems under an externally applied electrical-field through the dynamic equation of the kinkon-antikinkon pair. For ice, the mobility and the electrical conductivity of the proton transfer obtained are about 5.307×10^-7 m²  V^-1  s^-1 and 6.11×10^-4 Ω^-1 m^-1, respectively. The results obtained are in qualitative agreement with experimental data.     

Theory of the optical properties of phonon systems with disordered force constants,with application to NH4Cl

A theory of systems with substitutional disorder is presented. The theory treats off-diagonal disorder and is thus suitable for application to systems with disordered force constants. An example of such a system, to which particular consideration is given, is NH₄Cl, which has a disordered phase in which the force constants between NH₄⁺ ions are disordered because there are two equally probable orientations of an NH₄⁺ ion within a unit cell. The effect of disorder, in particular the breakdown of k-conservation, on the optical properties of such systems is studied via a calculation of the single-particle Green's function. Both the optical absorption and Raman cross section are shown to be related to the self-energy of this Green's function, and expressions for these quantities are obtained which are exact to second order in the ratio of order-dependent to non order-dependent force constants. The major qualitative features of the expression for the Raman cross section are found to be in good agreement with existing Raman scattering data on NH₄Cl.     

Pink noise of ionic conductance through single artificial nanopores revisited

We report voltage-clamp measurements through single conical nanopore obtained by chemical etching of a single ion track in polyimide film. Special attention is paid to the pink noise of the ionic current (i.e., 1/f noise) measured with different filling liquids. The relative pink-noise amplitude is almost independent of concentration and pH for KCl solutions, but varies strongly using ionic liquids. In particular, we show that depending on the ionic liquid, the transport of charge carriers is strongly facilitated (low noise and higher conductivity than in the bulk) or jammed. These results show that the origin of the pink noise can be ascribed neither to fluctuations of the pore geometry nor to the pore wall charges, but rather to a cooperative effect on ions motion in confined geometry.     

Glass-forming liquids,anomalous liquids,and polyamorphism in liquids and biopolymers

Summary Glass formation in nature and materials science is reviewed and the recent recognition of polymorphism within the glassy state, polyamorphism, is discussed. The process by which the glassy state originates during the continuous cooling or viscous slowdown process, is examined and the three canonical characteristics of relaxing liquids are correlated through the fragility. The conversion of strong liquids to fragile liquids by pressure-induced coordination number increases is discussed, and then it is shown that for the same type of system it is possible to have the same conversion accomplished via a first-order transition within the liquid state. The systems in which this can happen are of the same type which exhibit polyamorphism, and the whole phenomenology can be accounted for by a recent simple modification of the van der Waals model for tetrahedrally bonded liquids. The concept of complex amorphous systems which can lose a significant number of degrees of freedom through weak first-order transitions is then used to discuss the relation between native and denatured hydrated proteins, since the latter have much in common with plasticized chain polymer systems. Finally, we close the circle by taking a short-time-scale phenomenon given much attention by protein physicists,viz., the onset of an anomaly in the Debye-Waller factor with increasing temperature, and showing that for a wide variety of liquids, including computer-simulated strong and fragile ionic liquids, this phenomenon is closely correlated with the experimental glass transition temperature. This implies that the latter owes its origin to the onset of strong anharmonicity in certain components of the vibrational density of states (evidently related to the boson peak) which then permits the system to gain access to its configurational degrees of freedom. The more anharmonic these vibrational components, the closer to the Kauzmann temperature will commence the exploration of configuration space and, for a given configurational microstate degeneracy, the more fragile the liquid will be. Paper presented at the I International Conference on Scaling Concepts and Complex Fluids, Copanello, Italy, July 4–8, 1994.     

一维二元非对角关联无序体系跳跃电导特性

在单电子紧束缚无序模型基础上，建立了一维二元关联无序体系电子跳跃输运直流电导模型，并推导了其直流电导公式，通过计算其直流电导率，探讨了格点能量无序度、非对角关联及温度、外场对体系跳跃电导的影响.计算结果表明，一维二元无序体系的直流电导率随着格点能量无序度的增大而减小；当引入非对角关联时，体系出现退局域化现象，从而使体系的直流电导率增大；温度对体系的电子输运的影响表现为体系的直流电导率随温度的升高而增大；在外加电场的调制下，体系的直流电导率在强场区随电场强度增加而增长很快，呈现出非欧姆定律特性，但在弱场区外场的作用不明显. 关键词： 二元无序体系 跳跃电导 格点能量无序度 非对角关联     

On dielectrics of polymer electrolytes studied by impedance spectroscopy

We present a phenomenological view on dielectric relaxation in polymer electrolytes in the frequency range where conductivity is independent of frequency. Polymer electrolytes are seen as molecular mixtures of an organic polymer and an inorganic salt. The discussion applies also to ionic liquids. The following is based on systems with poly(ethylene oxide) (PEO) comprising the lithium perchlorate salt (LiClO₄) and also pure low-molecular PEO. In those systems, dipole-dipole interactions form an association/dissociation equilibrium which rules properties of the system in the low-frequency region. It turns out that effective concentration, c _S, of relaxing species provides a suitable variable for discussing electrochemical behavior of the electrolytes. Quantity c _S is proportional to the ratio of DC conductivity and mobility. Polymer salt mixtures form weak electrolytes. However, diffusion coefficient and corresponding molar conductivity display the typical (c _S)^1/2 dependence as well known from strong electrolytes, due to the low effective concentration c _S.     

Vibrational spectrum of topologically disordered systems

The topological nature of the disorder of glasses and supercooled liquids strongly affects their high-frequency dynamics. In order to understand its main features, we analytically studied a simple topologically disordered model, where the particles oscillate around randomly distributed centers, interacting through a generic pair potential. We present results of a resummation of the perturbative expansion in the inverse particle density for the dynamic structure factor and density of states. This gives accurate results for the range of densities found in real systems.     

Ionic liquids in external electric and electromagnetic fields: a molecular dynamics study

The non-thermal effects of external electric and electromagnetic fields in the microwave to far-infrared frequency range and at (r.m.s.) electric field intensities of 10^?3 to 0.25?V/Å_r.m.s. on neat salts of 1,3-dimethyl-imidazolium hexafluorophosphate ([dmim][PF₆]) and 1-butyl-3-methyl-imidazolium hexafluorophosphate ([bmim][PF₆]) have been investigated by means of non-equilibrium molecular dynamics simulation. Significant alterations in molecular mobility were found vis-à-vis zero-field conditions. Using Green–Kubo and transient time correlation function analysis, the electrical conductivity of these ionic liquids has been estimated. The results indicate that ionic liquids respond most significantly to frequencies much lower than those of smaller polar solvents such as water, although the mechanism of the field response is almost exclusively translational.     

Zero field Wigner crystal

A candidate for the insulating phase of the 2D electron gas, seen in high mobility 2D MOSFETS and heterojunctions, is a Wigner crystal pinned by the incipient disorder. With this in view, we study the effect of collective pinning on the physical properties of the crystal formed in zero external magnetic field. We use an elastic theory to describe to long wavelength modes of the crystal. The disorder is treated using the standard Gaussian variational method. We calculate various physical properties of the system with particular emphasis on their density dependence. We revisit the problem of compressibility in this system and present results for the compressibility obtained via effective capacitance measurements in experiments using bilayers. We present results for the dynamical conductivity, surface acoustic wave anomalies and the power radiated by the crystal through phonon emission at finite temperatures.     

Fractional variant of Stokes–Einstein relation in aqueous ionic solutions under external static electric fields

Both ionic solutions under an external applied static electric field E and glassy-forming liquids under undercooled state are in non-equilibrium state.In this work,molecular dynamics(MD)simulations with three aqueous alkali ion chloride(NaCl,KCl,and RbCl)ionic solutions are performed to exploit whether the glass-forming liquid analogous fractional variant of the Stokes–Einstein relation also exists in ionic solutions under E.Our results indicate that the diffusion constant decouples from the structural relaxation time under E,and a fractional variant of the Stokes–Einstein relation is observed as well as a crossover analogous to the glass-forming liquids under cooling.The fractional variant of the Stokes–Einstein relation is attributed to the E introduced deviations from Gaussian and the nonlinear effect.     

Fluorescent Probe Studies of Polarity and Solvation within Room Temperature Ionic Liquids: A Review

Ionic liquids display an array of useful and sometimes unconventional, solvent features and have attracted considerable interest in the field of green chemistry for the potential they hold to significantly reduce environmental emissions. Some of these points have a bearing on the chemical reactivity of these systems and have also generated interest in the physical and theoretical aspects of solvation in ionic liquids. This review presents an introduction to the field of ionic liquids, followed by discussion of investigations into the solvation properties of neat ionic liquids or mixed systems including ionic liquids as a major or minor component. The ionic liquid based multicomponent systems discussed are composed of other solvents, other ionic liquids, carbon dioxide, surfactants or surfactant solutions. Although we clearly focus on fluorescence spectroscopy as a tool to illuminate ionic liquid systems, the issues discussed herein are of general relevance to discussions of polarity and solvent effects in ionic liquids. Transient solvation measurements carried out by means of time-resolved fluorescence measurements are particularly powerful for their ability to parameterize the kinetics of the solvation process in ionic liquids and are discussed as well.     

Classical Representation of a Quantum System at Equilibrium

A quantum system at equilibrium is represented by a corresponding classical system, chosen to reproduce the thermodynamic and structural properties. The objective is to develop a means for exploiting strong coupling classical methods (e.g., MD, integral equations, DFT) to describe quantum systems. The classical system has an effective temperature, local chemical potential, and pair interaction that are defined by requiring equivalence of the grand potential and its functional derivatives with respect to the external and pair potentials for the classical and quantum systems. Practical inversion of this mapping for the classical properties is effected via the hypernetted chain approximation, leading to representations as functionals of the quantum pair correlation function. As an illustration, the parameters of the classical system are determined approximately such that ideal gas and weak coupling RPA limits are preserved (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Predicting the viscosity and electrical conductivity of ionic liquids on the basis of theoretically calculated ionic volumes

Selected physical properties of the ionic liquids might be quantitatively predicted based on the volumes of the ions these systems are composed of. It is demonstrated that the ionic volumes calculated using relatively simple theoretical quantum chemistry methods can be utilised to estimate the viscosities and electrical conductivities of various commonly used ionic liquids. The fitting formulas of the exponential form are offered and their predictive usefulness is verified. The quality of such predictions is discussed on the basis of several ionic liquids involving [Tf₂N]^? and [BF₄]^? anions and 16 various cations. The dependence of the viscosity and electrical conductivity of the ionic liquids on the temperature is also investigated and the temperature-dependent equations are derived and compared to the experimentally measured values.