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Bo Jönsson

Professor emeritus

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Attractive ion-ion correlation forces and the dielectric approximation

Author

  • Luis Pegado
  • Bo Jönsson
  • Håkan Wennerström

Summary, in English

We analyze the classical problem of the interaction between two charged surfaces separated by a solution containing neutralizing counter-ions. The focus is on obtaining a description where the solvent is treated explicitly rather than through a dielectric approximation as is conventionally done. We summarize the results of three papers where we have used a Stockmayer fluid model in Monte Carlo simulations. It is shown that the attractive ion-ion correlation mechanism is also operating when the solvent is described explicitly. There appears an oscillatory component to the force, but when this is accounted for, there is a semi-quantitative agreement between the continuum model and the model with explicit solvent. The properties of the continuum model can be reached in a molecular system by making the solvent molecules much smaller than the ions. It is demonstrated that having an explicit solvent model makes the analysis of force mechanisms more delicate due to the interplay between several different microscopic contributions to the force. Finally, it is argued that the agreement between the forces calculated using the continuum and the explicit solvent models, respectively, has as its basis the circumstance that the force between the surfaces is mainly caused by long-range ion-ion interactions, for which the dielectric approximation is most adequate. This argument applies equally well to an aqueous system as to the Stockmayer fluid.

Department/s

  • Computational Chemistry
  • Physical Chemistry

Publishing year

2016

Language

English

Pages

1-8

Publication/Series

Advances in Colloid and Interface Science

Document type

Journal article

Publisher

Elsevier

Topic

  • Theoretical Chemistry (including Computational Chemistry)

Keywords

  • Dielectric approximation
  • Double layer forces
  • Ion-ion correlations
  • Molecular solvent
  • Monte Carlo simulations

Status

Published

ISBN/ISSN/Other

  • ISSN: 0001-8686