Estimating the entropy of liquids from atom–atom radial distribution functions: silica,beryllium fluoride and water

Molecular dynamics simulations of water, liquid beryllium fluoride and silica melt are used to study the accuracy with which the entropy of ionic and molecular liquids can be estimated from atom–atom radial distribution function data. The pair correlation entropy is demonstrated to be sufficiently accurate that the density–temperature regime of anomalous behaviour as well as the strength of the entropy anomaly can be predicted reliably for both ionic melts as well as different rigid-body pair potentials for water. Errors in the total thermodynamic entropy for ionic melts due to the pair correlation approximation are of the order of 10% or less for most state points, but can be significantly larger in the anomalous regime at very low temperatures. In the case of water, the rigid-body constraints result in larger errors in the pair correlation approximation, between 20 and 30%, for most state points. Comparison of the excess entropy, S _e, of ionic melts with the pair correlation entropy, S ₂, shows that the temperature dependence of S _e is well described by T ^?2/5 scaling across both the normal and anomalous regimes, unlike in the case of S ₂. The residual multiparticle entropy, ΔS = S _e ? S ₂, shows a strong negative correlation with tetrahedral order in the anomalous regime.     

Polarization effects in ionic solids and melts

Ionic solids and melts are compounds in which the interactions are dominated by electrostatic effects. However, the polarization of the ions also plays an important role in many respects as has been clarified in recent years thanks to the development of realistic polarizable interaction potentials. After detailing these models, we illustrate the importance of polarization effects on a series of examples concerning the structural properties, such as the stabilization of particular crystal structures or the formation of highly-coordinated multivalent ions in the melts, as well as the dynamic properties such as the diffusion of ionic species. The effects on the structure of molten salt interfaces (with vacuum and electrified metal) is also described. Although most of the results described here concern inorganic compounds (molten fluorides and chlorides, ionic oxides...), the particular case of the room-temperature ionic liquids, a special class of molten salts in which at least one species is organic, will also be briefly discussed to indicate how the ideas gained from the study of ‘simple’ molten salts are being transferred to these more complex systems.     

A GMSA calculation of the radial distribution functions of molten RbCl

Summary The generalized mean spherical approximation (GMSA) for a fluid of charged hard spheres of equal diameters is used for calculating the radial distribution functions of molten RbCl. The results are compared to neutron diffraction data and a good overall agreement is found between the experimental and the theoreticalg _ij (r). Further application of this same approach to the case of ionic melts with ionic species of different diameters is discussed. Work supported in part by Comitato Regionale Ricerche Nucleari and Struttura della Materia (CRRNSM), Sicily, Italy.     

Thermodynamic perturbation theory for multipolar and ionic liquids

We extend earlier work of ours on the use of Padé approximants in the theory of multipolar and ionic potentials. The new features are (i) extension of our work to mixed multipole terms and inclusion of polarizability, (ii) formulation and implementation of a systematic means of getting analytic approximations for all the two-body and three-body terms appearing in the theory, (iii) assessment of the ionic Padé results in the low-concentration region important in ionic-solution applications, (iv) use of the Padé in a mixed perturbation theory of improved accuracy in that low-concentration regime. The results of (iii) and (iv) are used to study the remarkable lowdensity charged-sphere critical point recently discovered by Stell, Wu, and Larsen.     

Melting of columnar hexagonal DNA liquid crystals

The persistence length DNA hexagonal-cholesteric phase transition upon dilution and/or increase in solvent ionic strength is investigated with polarized light microscopy. The ionic strength dependence of the transition follows Lindemann criterion , i.e., the hexagonal lattice melts when the root-mean-square fluctuations in transverse order exceed 10% of the interaxial spacing. The spacings are derived from density and the fluctuations are estimated with a theory of undulation enhanced electrostatic interactions. Additional support for this theory is given by the DNA equation of state and anisotropic neutron radiation scattering from magnetically aligned cholesteric samples just below the phase transition. Received: 17 November 1997 / Revised: 21 January 1998 / Accepted: 25 February 1998     

Electrical properties of unusual ionic melts

The paper reviews the advances that have been made in recent years in the understanding of electrical transport in fully ionized molten salts, partly dissociated molecular liquids and liquid ionic stoichiometric alloys like CsAu. Special emphasis is placed on the recently observed temperature and pressure induced gradual transition between the limiting cases of molecular insulators and ionic melts. At supercritical temperatures salts undergo a continuous transition from an insulating vapour to a highly conducting ionic fluid if the density is increased sufficiently. This transition is due to a shift of the ionization equilibrium between molecules and ions, in favour of the ions, with increasing density. Poorly conducting molten salts and polar substances like water and ammonia also become more ionic, and consequently better conductors, at very high pressures.

Recent thermodynamic, magnetic and electrical measurements on liquid alloys which are composed of two metallic elements and which are non-metallic at definite stoichiometric compositions are discussed. Special emphasis is placed on the liquid Cs-Au system which resembles in many respects the molten alkalimetal halides.     

高分辨显微镜纳米云纹方法的发展与应用

介绍了近年来发展的纳米云纹法及其新的应用。这些方法是基于原子力显微镜、扫描隧道显微镜和透射电子显微镜的原理提出来的。纳米云纹法能够对物体的微/纳观变形提供定量的分析。详述了这些方法的测量原理和实验技术,并进行了新的应用研究。实验结果论证了这些方法的可行性,并证实了这些方法具有纳米级的位移测量灵敏度。     

Painlevé analysis and integrability of the trapped ionic system

Integrability in the Painlevé sense of the trapped ionic system in the quadrupole field with superpositions of rotationally symmetric hexapole and octopole fields is studied. Five integrable cases of the system are reported. First Integrals of the planar motion are founded. Confirming three-dimensional integrability of the equations of motion, the third explicit integrals of motion are constructed directly for each case. We carried out a numerical study to observe the regularity and chaotic regions via the Poincaré surface of sections, and corroborate the analytical results.     

Solution of the Ornstein-Zernike equation for a mixture of hard ions and Yukawa closure

The solution of the Ornstein-Zernike equation with Yukawa closure discussed in an earlier paper is simplified and extended to the more general case of several exponentials with real or complex exponents. The interesting case of an ionic mixture with Yukawa closure is solved explicitly. This case corresponds to ionic melts (molten salts).Supported by the Center of Environment and Energy Research of the University of Puerto Rico, OCEGI, and in part by NSF grant CHE-77-14611.     

Formation and dispersion of an electrolyte film on an ice electrode melting as a result of Joule heat evolution

The thickness of a liquid film (≈3.6 μm) forming on an ice electrode is determined by solving the Stefan problem. The electrode melts as a result of Joule heat evolution when the current passes through it. The temperature distributions in the film and ice substrate are found. The radius of curvature of emitting asperities formed as a result of film instability against the surface charge is found to be ≈40 nm. This value provides the intense field evaporation of individual ions and ionic clusters from the top of the asperities at a potential difference of ≈100 V.     

Dynamics of SCN- ions in molten thiocyanates and aqueous solutions by Raman spectroscopy

The Raman spectra of the v ₁(CN) stretching mode of SCN^- ions have been measured in molten thiocyanates, KSCN and NaSCN, at temperatures 450-600K. The vibrational and the rotational correlation functions are calculated, and the dynamics of SCN^- ions in the molten state are compared with those in aqueous solutions of KSCN, NaSCN, and LiSCN at concentrations 1–10 mol dm^-3 and at temperatures 303–353 K. The observed vibrational correlation functions are analysed by the stochastic line shape theory of Kubo, in which homogeneous and inhomogeneous broadening are treated simultaneously. Both broadening contributions to the isotropic spectra are extracted. The homogeneous broadening is found to increase with increasing temperature in both melts and aqueous solutions; the inhomogeneous broadening remains constant in molten KSCN while it decreases in aqueous solutions. As the result, the isotropic Raman bandwidth is considered to increase with temperature in the molten state and to decrease in aqueous solutions. Rotational correlation functions of SCN^- ions in these molten salts show the behaviour of the short time inertial rotation (t ? 0·15 ps, jump angle 20°), which is a little slower than the free rotation of a single ion. The long time exponential decay of the rotational correlation functions reflects the ultimate diffusional behaviour of the ionic reorientation. The rotational relaxation rate increases with increasing temperature in both melts and aqueous solutions. The vibrational dephasing rate decreases and the rotational relaxation rate increases as the cation size increases in melts. In aqueous solutions, the vibrational dephasing rate follows the same cation dependence as that in melts, while the rotational relaxation rate decreases as the cation size increases. This seems to be a consequence of the specific local structures in aqueous electrolyte solutions.     

Relationship between solid state parameters and melting parameters for alkali halides

In the present communication we report some interesting relationships found between solid state parameters and melting parameters for alkali halides. Values of the melting temperatures and relative changes in volume after melting are found to exhibit systematic trend of variation with the Phillips ionicity parameter defining the amount of fractional ionic character. An empirical analysis is presented for determining the nearest-neighbour distances in alkali halide melts. The predictions made in the present work are shown to be consistent with available X-ray diffraction measurements.     

Approximation solution of the Dirac equation with position-dependent mass for the generalized Hulthén potential

The one-dimensional Dirac equation with position-dependent mass is approximately solved for the generalized Hulthén potential in the case of the smooth step mass distribution. The relativistic energy spectrum and two-component spinor wavefunctions are obtained by the function analysis method. Some interesting results including the standard one-dimensional Hulthén and Woods–Saxon potentials are also discussed.     

Interdiffusion in potassium-lead melts in a wide range of concentrations

Interdiffusion in potassium-lead melts containing 30, 40, 50, 66.7, and 84.4 at. % Pb was investigated using gamma-ray attenuation technique in the temperature range from 550 to 970 K. It was found that the concentration dependence of interdiffusion coefficient has a maximum in the vicinity of 40–50 at. % Pb. It was shown that this feature is associated with the trend of forming ionic complexes of K₄Pb₄ in liquid alloys.     

Effect of polymer architecture and ionic aggregation on the scattering peak in model ionomers

We perform molecular dynamics simulations of coarse-grained ionomer melts with two different architectures. Regularly spaced charged beads are placed either in the polymer backbone (ionenes) or pendant to it. The ionic aggregate structure is quantified as a function of the dielectric constant. The low wave vector ionomer scattering peak is present in all cases, but is significantly more intense for pendant ions, which form compact, discrete aggregates with liquidlike interaggregate order. This is in qualitative contrast to the ionenes, which form extended aggregates.     

Water and other tetrahedral liquids: order, anomalies and solvation

In order to understand the common features of tetrahedral liquids with water-like anomalies, the relationship between local order and anomalies has been studied using molecular dynamics simulations for three categories of such liquids: (a)?atomistic rigid-body models for water (TIP4P, TIP4P/2005, mTIP3P, SPC/E), (b)?ionic melts, BeF(2) (TRIM model) and SiO(2) (BKS potential) and (c)?Stillinger-Weber liquids parametrized to model water (mW) and silicon. Rigid-body, atomistic models for water and the Stillinger-Weber liquids show a strong correlation between tetrahedral and pair correlation order and the temperature for the onset of the density anomaly is close to the melting temperature. In contrast, the ionic melts show weaker and more variable degrees of correlation between tetrahedral and pair correlation metrics, and the onset temperature for the density anomaly is more than twice the melting temperature. In the case of water, the relationship between water-like anomalies and solvation is studied by examining the hydration of spherical solutes (Na(+), Cl(-), Ar) in water models with different temperature regimes of anomalies (SPC/E, TIP4P and mTIP3P). For both ionic and nonpolar solutes, the local structure and energy of water molecules is essentially the same as in bulk water beyond the second-neighbour shell. The local order and binding energy of water molecules are not perturbed by the presence of a hydrophobic solute. In the case of ionic solutes, the perturbation is largely localized within the first hydration shell. The binding energies for the ions are strongly dependent on the water models and clearly indicate that the geometry of the partial charge distributions, and the associated multipole moments, play an important role. However the anomalous behaviour of the water network has been found to be unimportant for polar solvation.     

Transport properties of PbSnI4

PbSnI₄ has been prepared from equimolar amounts of PbI₂ and SnI₂. X-ray and DSC measurements show the material to be uniphase in the temperature range 30 to 400°C; it has a tetragonal structure and melts at 379°C. The electrical conductivity is mainly ionic with an ionic transport number greater than 0.99 at 200°C. Conductivity at room temperature is 2.56 × 10⁻⁸ Ω⁻¹ cm⁻¹ while the value at 200°C is 1.25 × 10⁻⁶ Ω⁻¹ cm⁻¹.     

Lennard–Jones Lecture 2017* *

ABSTRACT

Some examples of the use of molecular dynamics simulation to study solutions of small molecules in ionic liquids are discussed. It is shown that electrostatic forces, while not the dominant solute–solvent interaction, determine the local solute environment. The solubility of aromatics and the changes in the spectra of low-frequency intermolecular vibrations in two related ionic liquids (one dicationic and one monocationic) are compared with experimental results and related to the local environment.     

Ionic photoconductivity of RbAg4I5 superionic crystals

A new effect of illumination on ionic conductivity and activation energy of migration of mobile Ag⁺ cations in RbAg₄I₅ superionic crystals has been detected and studied. Reversible changes in the ionic conductivity due to illumination of superionic crystals are caused by reversible changes in the structure of electronic centers caused by elastic strain around these centers. The effect of elastic deformation on the process of ionic transport and activation energy for diffusion of mobile silver cations has been studied. Photostimulated recovery of the ionic conductivity after its change due to preliminary illumination of a RbAg₄I₅ superionic crystal with light of wavelength λ≃430 nm has been detected. This recovery of the ionic conductivity is due to excitation of centers in complexes generated by previous illumination of tested samples. Zh. éksp. Teor. Fiz. 112, 698–706 (August 1997)