The decay of pair correlation functions in ionic fluids: A dressed ion theory analysis of Monte Carlo simulations

Ulander, Johan; Kjellander, Roland

doi:10.1063/1.1350449

Cited by 41 publications

(64 citation statements)

References 25 publications

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“…In particular, this potential has been shown previously [36] to correctly describe the qualitative features of the -transition in simple electrolytes [37][38][39]. It also has proved successful in the description of phase separation in polyelectrolyte solutions [40].…”

Section: ͑1͒mentioning

confidence: 92%

Phase diagram of charged dumbbells: A random phase approximation approach

2004

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The phase diagram of the charged hard dumbbell system (hard spheres of opposite unit charge fixed at contact) is obtained with the use of the random phase approximation (RPA). The effect of the impenetrability of charged spheres on charge-charge fluctuations is described by introduction of a modified electrostatic potential. The correlations of ions in a pair are included via a correlation function in the RPA. The coexistence curve is in good agreement with Monte Carlo simulations. The relevance of the theory to the restricted primitive model is discussed.

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Section: ͑1͒mentioning

confidence: 92%

Phase diagram of charged dumbbells: A random phase approximation approach

2004

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“…19,20,32 Since the dress is only a part of ρ j , we have in general dr ρ dress j (r) = −q j , which implies that q * j ≡ dr ρ * j (r) = 0. An ion in the bulk electrolyte is surrounded by an ion cloud of charge density ρ j (r), which has a total charge that is of opposite sign to q j and neutralizes the latter, dr ρ j (r) = −q j (the condition of local electroneutrality).…”

Section: Nonlocal Electrostatics and Polarization Response In The Taimentioning

confidence: 99%

Decay behavior of screened electrostatic surface forces in ionic liquids: the vital role of non-local electrostatics

Kjellander

2016

Phys. Chem. Chem. Phys.

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Screened electrostatic surface forces, also called double layer forces, between surfaces in ionic liquids can, depending on the circumstances, decay in an exponentially damped, oscillatory manner or in a plain exponential way (the latter as in dilute electrolyte solutions where ion-ion correlations are very weak). The occurrence of both of these behaviors in dense ionic liquids, where ion-ion correlations are very strong, is analyzed in the current work using exact statistical mechanics formulated in a manner that is physically transparent. A vital ingredient in understanding the decay behaviors is the fact that electrostatics in dense electrolytes have a non-local nature caused by the strong correlations. It is shown that the effects of non-locality can be elucidated by a remarkably simple, general expression for the decay parameter κ that replaces the classical expression for the inverse Debye length κDH of the Debye-Hückel (DH) and non-linear Poisson-Boltzmann approximations. This exact expression is valid for both the plain exponential and the oscillatory cases. It shows how strong correlations can give rise to plain exponential decay with a long decay length. Such a decay can arise from anion-cation associations of various kinds, for instance transient ion pairing or association caused by many-body correlations; ion pairing is a possibility but not a necessity for this to occur. Theoretical analysis is done for systems consisting of ions with an arbitrary shape and internal charge density and immersed planar walls with arbitrary internal charge distribution and any short-range ion-surface interaction. The screened electrostatic surface force between two walls is at large separations proportional to the product of effective surface charge densities of each wall. For the oscillatory case, each wall contributes with a phase shift to the oscillations of the interaction.

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“…Investigations of the hypernetted chain (HNC) equation [8,[26][27][28] indicate that y C is dependent on the electrolyte valence. Also, from diagrammatic techniques [29] and dressed ion theory [30], the asymptotic behaviour of the screening length for small values of the coupling parameter Γ = βκe 2 /4πε 0 ε r , e elementary unit of charge, has a purely electrostatic contribution for a → 0.…”

Section: Discussionmentioning

confidence: 99%

A modified Poisson-Boltzmann approach to homogeneous ionic solutions

Outhwaite¹

2004

Condens. Matter Phys.

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The mean electrostatic potential approach to ionic solutions was initiated by the mean field work of Gouy and Chapman for inhomogeneous systems, and Debye and Hückel for bulk solutions. Any successful extension of the mean field theories requires an adequate treatment of both the exclusion volume and fluctuation terms. One such development has been the modified Poisson-Boltzmann approach. Although the bulk modified PoissonBoltzmann theory was introduced 35 years ago, only a limited amount of work has been put into its development due to the successful application of liquid state theories to ionic systems. We outline here the bulk modified Poisson-Boltzmann equation, comment on some of its successes, and mention some outstanding problems.

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The decay of pair correlation functions in ionic fluids: A dressed ion theory analysis of Monte Carlo simulations

Cited by 41 publications

References 25 publications

Phase diagram of charged dumbbells: A random phase approximation approach

Phase diagram of charged dumbbells: A random phase approximation approach

Decay behavior of screened electrostatic surface forces in ionic liquids: the vital role of non-local electrostatics

A modified Poisson-Boltzmann approach to homogeneous ionic solutions

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