The behavior of ions near a charged wall-dependence on ion size, concentration, and surface charge.

Jesse J. Howard, John S. Perkyns, Bernard Pettitt

Research output: Contribution to journalArticle

39 Citations (Scopus)

Abstract

A renormalization of the 3D-RISM-HNC integral equation is used to study the solvent and ion distributions at neutral and negatively charged planar atomistic surfaces. The charge density of the surfaces ranged from 0.0 to 0.4116 C/m2, and the modeled electrolyte solutions consist of the salts NaCl, KCl, and CsCl at concentrations of 0.1, 0.25, and 1.0 M in SPC/E water. The results are qualitatively compared to the results from other integral equation methods and simulations for similar models. We find that the 3D-IEs predict an electric multilayer screening behavior in the solvent and ion distributions in contrast to the double layer anticipated from Poisson-Boltzmann theory. It is observed that the cation size has a significant effect on the distributions near the surface up to three solvation layers beyond which the behavior is the same among the different cations. The response of the distributions to the charged surface is described as an increase in ion and solvent density near the wall. The higher concentration solutions screen the electrostatic source more strongly at the wall as expected. The importance of ion-solvent and ion-ion correlations near the surface is shown through three-body correlation functions which are obtainable from the 3D-IEs in this study.

Original languageEnglish (US)
Pages (from-to)6074-6083
Number of pages10
JournalJournal of Physical Chemistry B
Volume114
Issue number18
DOIs
StatePublished - May 13 2010
Externally publishedYes

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Surface charge
Ions
ion distribution
ions
integral equations
Integral equations
Cations
cations
Positive ions
Solvation
solvation
Charge density
screening
Electrolytes
electrolytes
Electrostatics
electrostatics
Screening
Multilayers
salts

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Materials Chemistry
  • Surfaces, Coatings and Films

Cite this

The behavior of ions near a charged wall-dependence on ion size, concentration, and surface charge. / Howard, Jesse J.; Perkyns, John S.; Pettitt, Bernard.

In: Journal of Physical Chemistry B, Vol. 114, No. 18, 13.05.2010, p. 6074-6083.

Research output: Contribution to journalArticle

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