Mean-Field Theory of Electrical Double Layer In Ionic Liquids with Account of Short-Range Correlations

Goodwin, Zachary A. H.; Feng, Guang; Kornyshev, Alexei A.

doi:10.1016/j.electacta.2016.12.092

Cited by 145 publications

(202 citation statements)

References 78 publications

Supporting

Mentioning

190

Contrasting

Order By: Relevance

“…They give a possibility to consider systems beyond the assumptions of continuum models and to take into account a wide spectrum of interparticle interactions as well as to predict correlation effects using the statistical mechanics. It was shown that the voltage dependence of the differential capacitance obtained within the mean field approximation for the case of short-range interactions between ions is closer to experimental findings [47,48]. The importance of short-range interactions in a lattice model of ionic systems was demonstrated in [49], where the effect of competition between long-range Coulomb and short-range dispersion interaction on phase transitions was studied.…”

Section: Introductionsupporting

confidence: 56%

The effect of short-range interaction and correlations on the charge and electric field distribution in a model solid electrolyte

et al. 2019

View full text Add to dashboard Cite

A simple lattice model of a solid electrolyte presented as a xy-slab geometry system of mobile cations on a background of energetic landscape of the host system and a compensating field of uniformly distributed anions is studied. The system is confined in the z-direction between two oppositely charged walls, which are in parallel to xy-plane. Besides the long-range Coulomb interactions appearing in the system, the short-range attractive potential between cations is considered in our study. We propose the mean field description of this model and extend it by taking into account correlation effects at short distances. Using the free energy minimization at each of z-coordinates, the corresponding set of non-linear equations for the chemical potential is derived. The set of equations was solved numerically with respect to the charge density distribution in order to calculate the cations distribution profile and the electrostatic potential in the system along z-direction under different conditions. An asymmetry of charge distribution profile with respect to the midplane of the system is observed. The effects of the short-range interactions and pair correlations on the charge and electric field distributions are demonstrated.

show abstract

Section: Introductionsupporting

confidence: 56%

The effect of short-range interaction and correlations on the charge and electric field distribution in a model solid electrolyte

et al. 2019

View full text Add to dashboard Cite

show abstract

“…Extremely high ion concentrations in ionic liquids strongly increase the importance of short-range interactions and correlations. It was shown that with accounting of the short-range interactions on the mean field level in addition to the Coulomb ones the voltage dependence of the differential capacitance becomes closer to experimental findings [24,25]. An important influence of a competition of short-range dispersion (or van der Waals) and long-range Coulomb interactions on phase transitions in a lattice model of ionic systems was demonstrated in [26].…”

Section: Introductionmentioning

confidence: 61%

Short- and long-range contributions to equilibrium and transport properties of solid electrolytes

Bokun¹,

Kravtsiv²,

Holovko³

et al. 2019

Condens. Matter Phys.

View full text Add to dashboard Cite

Condensed ionic systems are described in the framework of a combined approach that takes into account both long-range and short-range interactions. Short-range interaction is expressed in terms of mean potentials and long-range interaction is considered in terms of screening potentials. A system of integral equations for these potentials is constructed based on the condition of the best agreement of the system of study with the reference system. In contrast to the description of media with short-range interactions, in this text the reference distribution includes not only the field of mean potentials but also Coulomb interaction between particles. A one-component system made of ions in a neutralizing background of fixed counterions is considered. The model can be used to describe solid ionic conductors. In order to study the movement of cations on the sites of their sub-lattice, the lattice approximation of the theory is employed based on the calculation of the pair distribution function. Using the collective variables approach, a technique improving the starting expression for this function is proposed. Notably, the neglected terms in the expansion of this function are approximated by single-particle terms ensuring that the normalization condition is satisfied. As a result, the applicability of the theory is extended to a wide region of thermodynamic parameters. The chemical potential and the diffusion coefficient are calculated showing the possibility of phase transitions characteristic of the system.

show abstract

“…and taking the integral (41), we arrive at the following relation for the density of the electrostatic free energy…”

Section: System Of Dipolar Hard Spheresmentioning

confidence: 99%

Nonlocal density functional theory of water taking into account many-body dipole correlations: binodal and surface tension of ‘liquid–vapour’ interface

Budkov

Kolesnikov

2020

J. Phys.: Condens. Matter

View full text Add to dashboard Cite

In this paper we formulate a nonlocal density functional theory of inhomogeneous water. We model a water molecule as a couple of oppositely charged sites. The negatively charged sites interact with each other through the Lennard–Jones potential (steric and dispersion interactions), square-well potential (short-range specific interactions due to electron charge transfer), and Coulomb potential, whereas the positively charged sites interact with all types of sites by applying the Coulomb potential only. Taking into account the nonlocal packing effects via the fundamental measure theory, dispersion and specific interactions in the mean-field approximation, and electrostatic interactions at the many-body level through the random phase approximation, we describe the liquid–vapour interface. We demonstrate that our model without explicit account of the association of water molecules due to hydrogen bonding and with explicit account of the electrostatic interactions at the many-body level is able to describe the liquid–vapour coexistence curve and the surface tension at the ambient pressures and temperatures. We obtain very good agreement with available in the literature MD simulation results for density profile of liquid–vapour interface at ambient state parameters. The formulated theory can be used as a theoretical background for describing of the capillary phenomena, occurring in micro- and mesoporous materials.

show abstract

Mean-Field Theory of Electrical Double Layer In Ionic Liquids with Account of Short-Range Correlations

Cited by 145 publications

References 78 publications

The effect of short-range interaction and correlations on the charge and electric field distribution in a model solid electrolyte

The effect of short-range interaction and correlations on the charge and electric field distribution in a model solid electrolyte

Short- and long-range contributions to equilibrium and transport properties of solid electrolytes

Nonlocal density functional theory of water taking into account many-body dipole correlations: binodal and surface tension of ‘liquid–vapour’ interface

Contact Info

Product

Resources

About