Journal ArticleDOI
Electrical properties of polarizable ionic solutions. I. Theoretical aspects
TLDR
In this article, the authors generalize previous work on the relation between the frequency-dependent dielectric constant and conductivity and time correlation functions of electrical current and polarization in electrolyte solutions by allowing the ions and solvent molecules to be polarizable.Abstract:
We generalize previous work [J. Chem. Phys. 85, 6645 (1986)] on the relation between the frequency‐dependent dielectric constant and conductivity and time correlation functions of electrical current and polarization in electrolyte solutions by allowing the ions and solvent molecules to be polarizable. Detailed results are given for the infinite system (no boundary), spherical system embedded in a continuum and periodic boundary conditions. The Stillinger–Lovett (SL) sum rules are derived for these geometries. It is shown, in particular, that they provide a means of calculating the high frequency dielectric constant in a molecular dynamics simulation. A test of the phenomenological coefficient‐susceptibility relations and the SL conditions is presented in part II by performing molecular dynamics simulations on a model electrolyte solution with different boundary conditions.read more
Citations
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An explanation for the charge on water’s surface
TL;DR: A Hamaker-like force on the hydroxide ion is shown that attracts it to regions where dipole-moment fluctuations are smaller than in bulk water, in other words, to regions of low relative permittivity.
Journal ArticleDOI
Calculation of the dielectric properties of a protein and its solvent: theory and a case study
TL;DR: In this article, the authors present a rigorous derivation of a theory for the calculation of the frequency-dependent dielectric properties of each component of the system protein/water/ions.
Journal ArticleDOI
Polarization effects in ionic solids and melts
Mathieu Salanne,Paul A. Madden +1 more
TL;DR: In this paper, 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 diffusion of ionic species is discussed.
Journal ArticleDOI
Polarization effects in ionic solids and melts
Mathieu Salanne,Paul A. Madden +1 more
TL;DR: In this article, the authors illustrate the importance of polarization effects on a series of examples concerning the structural properties, such as 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.
Journal ArticleDOI
On the computation and contribution of conductivity in molecular ionic liquids
TL;DR: This study works out the theoretical framework necessary to compute the conductivity spectrum and its low frequency limit of ionic liquids and discusses the frequency dependence of the cross correlation between the collective rotational dipole moment and the current.
References
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Journal ArticleDOI
Theory of Electric Polarization
Journal ArticleDOI
Simulation of electrostatic systems in periodic boundary conditions. I. Lattice sums and dielectric constants.
TL;DR: In this paper, the effective interactions of ions, dipoles and higher-order multipoles under periodic boundary conditions are calculated where the array of periodic replications forms an infinite sphere surrounded by a vacuum.
Journal ArticleDOI
A polarizable model for water using distributed charge sites
Michiel Sprik,Michael L. Klein +1 more
TL;DR: In this article, an algorithm for treating many body polarization effects that is suitable for molecular dynamics simulations of polar fluids is proposed, and the effective dipole moment of a water molecule in water is found to be 2.85 D. As an application of the procedure, they have augmented an existing point charge model for water.
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General Restriction on the Distribution of Ions in Electrolytes
TL;DR: In this article, the second-moment condition was generalized to arbitrary mixtures of electrolytes of unrestricted charge species, and the condition remains valid even in the presence of specific chemical interactions that lead to complex ion formation.
Journal ArticleDOI
Theoretical calculation of ionic solution properties
TL;DR: In this article, a model system of electrolyte solution is studied by molecular dynamics simulation and the results show how the polarizability of the molecules and the ratio of the molecular diameters of the ions and solvent molecules affect the properties of the system.