2008The Journal of Chemical PhysicsRequires access

Ion-ion correlation attraction in a molecular solvent

Luís Pegado, Bo Jönsson, Håkan Wennerström

Open publisher page 22 citations

Abstract

We have performed Monte Carlo simulations for two like-charged infinite plates with counterions and solvent in between. The solvent is described at the primitive model (PM) level and also as a Stockmayer fluid. Both descriptions share the same qualitative ion correlation picture. At sufficiently high coupling, the pressure between the plates shows an attractive minimum, which is lost or reduced upon decreasing counterion valency, surface charge density, or increasing the screening. The pressure profiles become more oscillatory with higher density, which masks the ion-ion correlation attraction. An interpretation in terms of interaction free energies rather than pressures clarifies the picture. Analyzing the different contributions to the pressure gives further support to the conclusions; the same components are responsible for the same effect in the PM and in the molecular solvent.

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What this paper is about

We have performed Monte Carlo simulations for two like-charged infinite plates with counterions and solvent in between. The solvent is described at the primitive model (PM) level and also as a Stockmayer fluid. Both descriptions share the same qualitative ion correlation picture. At sufficiently high coupling, the pressure between the plates shows an attractive minimum, which is lost or reduced upon decreasing counterion valency, surface charge density, or increasing the screening. The pressure profiles become more oscillatory with higher density, which masks the ion-ion correlation attraction. An interpretation in terms of interaction free energies rather than pressures clarifies the picture. Analyzing the different contributions to the pressure gives further support to the conclusions; the same components are responsible for the same effect in the PM and in the molecular solvent.

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Available abstract

We have performed Monte Carlo simulations for two like-charged infinite plates with counterions and solvent in between. The solvent is described at the primitive model (PM) level and also as a Stockmayer fluid. Both descriptions share the same qualitative ion correlation picture. At sufficiently high coupling, the pressure between the plates shows an attractive minimum, which is lost or reduced upon decreasing counterion valency, surface charge density, or increasing the screening. The pressure profiles become more oscillatory with higher density, which masks the ion-ion correlation attraction. An interpretation in terms of interaction free energies rather than pressures clarifies the picture. Analyzing the different contributions to the pressure gives further support to the conclusions; the same components are responsible for the same effect in the PM and in the molecular solvent.

Key concepts: Valency, Counterion, Ion, Solvent, Attraction, Chemical physics, Chemistry, Monte Carlo method

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