A simple correlationcorrected PoissonBoltzmann theory
(2004) In The Journal of Physical Chemistry Part B 108(26). p.92369245 Abstract
 A simple approach is used to introduce effects of ionion correlations into the PoissonBoltzmann theory. The meanfield 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 PoissonBoltzmann theory, is accounted for by this effective potential. We show that important phenomena due to ionion correlations, such as net attraction between surfaces of like charge and charge reversal in double layer systems, are qualitatively and serniquantitatively reproduced by this correlationcorrected theory, which contains no... (More)
 A simple approach is used to introduce effects of ionion correlations into the PoissonBoltzmann theory. The meanfield 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 PoissonBoltzmann theory, is accounted for by this effective potential. We show that important phenomena due to ionion correlations, such as net attraction between surfaces of like charge and charge reversal in double layer systems, are qualitatively and serniquantitatively reproduced by this correlationcorrected 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 meanfield 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 PoissonBoltzmann theory. (Less)
Please use this url to cite or link to this publication:
http://lup.lub.lu.se/record/139642
 author
 Forsman, Jan ^{LU}
 organization
 publishing date
 2004
 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
 15205207
 DOI
 10.1021/jp049571u
 language
 English
 LU publication?
 yes
 id
 3dae32fa7dae4c2abd47989de24c8724 (old id 139642)
 date added to LUP
 20070717 09:20:53
 date last changed
 20181121 20:40:46
@article{3dae32fa7dae4c2abd47989de24c8724, abstract = {A simple approach is used to introduce effects of ionion correlations into the PoissonBoltzmann theory. The meanfield 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 PoissonBoltzmann theory, is accounted for by this effective potential. We show that important phenomena due to ionion correlations, such as net attraction between surfaces of like charge and charge reversal in double layer systems, are qualitatively and serniquantitatively reproduced by this correlationcorrected 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 meanfield 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 PoissonBoltzmann theory.}, author = {Forsman, Jan}, issn = {15205207}, language = {eng}, number = {26}, pages = {92369245}, publisher = {The American Chemical Society}, series = {The Journal of Physical Chemistry Part B}, title = {A simple correlationcorrected PoissonBoltzmann theory}, url = {http://dx.doi.org/10.1021/jp049571u}, volume = {108}, year = {2004}, }