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A simple correlation-corrected Poisson-Boltzmann theory

Forsman, Jan LU (2004) In The Journal of Physical Chemistry Part B 108(26). p.9236-9245
Abstract
A simple approach is used to introduce effects of ion-ion correlations into the Poisson-Boltzmann theory. The mean-field character of the theory is retained and correlations are approximated by an effective interaction potential, which differs from the Coulombic at short range. In particular, the severe overestimation of the average interaction energy between ions of like charge inherent in the original Poisson-Boltzmann theory, is accounted for by this effective potential. We show that important phenomena due to ion-ion correlations, such as net attraction between surfaces of like charge and charge reversal in double layer systems, are qualitatively and serniquantitatively reproduced by this correlation-corrected theory, which contains no... (More)
A simple approach is used to introduce effects of ion-ion correlations into the Poisson-Boltzmann theory. The mean-field character of the theory is retained and correlations are approximated by an effective interaction potential, which differs from the Coulombic at short range. In particular, the severe overestimation of the average interaction energy between ions of like charge inherent in the original Poisson-Boltzmann theory, is accounted for by this effective potential. We show that important phenomena due to ion-ion correlations, such as net attraction between surfaces of like charge and charge reversal in double layer systems, are qualitatively and serniquantitatively reproduced by this correlation-corrected theory, which contains no adjustable parameter. The response of net surface interactions to the addition of salt is also captured by the theory and satisfactory quantitative agreement is found with simulation results, even at molar concentrations of divalent salt and in the presence of highly charged surfaces. The mean-field theory is furthermore able to qualitatively predict the way in which bulk salt properties such as the osmotic coefficient and the excess chemical potential depend on the salt concentration. The quantitative performance is poorer than for electric double layer systems, but there is still a substantial improvement relative to the ordinary Poisson-Boltzmann theory. (Less)
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author
organization
publishing date
type
Contribution to journal
publication status
published
subject
in
The Journal of Physical Chemistry Part B
volume
108
issue
26
pages
9236 - 9245
publisher
The American Chemical Society
external identifiers
  • wos:000222279100069
  • scopus:3142704441
ISSN
1520-5207
DOI
10.1021/jp049571u
language
English
LU publication?
yes
id
3dae32fa-7dae-4c2a-bd47-989de24c8724 (old id 139642)
date added to LUP
2007-07-17 09:20:53
date last changed
2017-09-03 04:35:56
@article{3dae32fa-7dae-4c2a-bd47-989de24c8724,
  abstract     = {A simple approach is used to introduce effects of ion-ion correlations into the Poisson-Boltzmann theory. The mean-field character of the theory is retained and correlations are approximated by an effective interaction potential, which differs from the Coulombic at short range. In particular, the severe overestimation of the average interaction energy between ions of like charge inherent in the original Poisson-Boltzmann theory, is accounted for by this effective potential. We show that important phenomena due to ion-ion correlations, such as net attraction between surfaces of like charge and charge reversal in double layer systems, are qualitatively and serniquantitatively reproduced by this correlation-corrected theory, which contains no adjustable parameter. The response of net surface interactions to the addition of salt is also captured by the theory and satisfactory quantitative agreement is found with simulation results, even at molar concentrations of divalent salt and in the presence of highly charged surfaces. The mean-field theory is furthermore able to qualitatively predict the way in which bulk salt properties such as the osmotic coefficient and the excess chemical potential depend on the salt concentration. The quantitative performance is poorer than for electric double layer systems, but there is still a substantial improvement relative to the ordinary Poisson-Boltzmann theory.},
  author       = {Forsman, Jan},
  issn         = {1520-5207},
  language     = {eng},
  number       = {26},
  pages        = {9236--9245},
  publisher    = {The American Chemical Society},
  series       = {The Journal of Physical Chemistry Part B},
  title        = {A simple correlation-corrected Poisson-Boltzmann theory},
  url          = {http://dx.doi.org/10.1021/jp049571u},
  volume       = {108},
  year         = {2004},
}