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Effective interaction potentials for alkali and alkaline earth metal ions in SPC/E water and prediction of mean ion activity coefficients

Gavryushov, Sergei LU and Linse, Per LU (2006) In The Journal of Physical Chemistry Part B 110(22). p.10878-10887
Abstract
The potential of mean force (PMF) acting between two simple ions surrounded by SPC/E water have been determined by molecular dynamics (MD) simulations using a spherical cavity approach. Such effective ion-ion potentials were obtained for Me-Me, Me-Cl-, and Cl--Cl- pairs, where Me is a Li+, Na+, K+, Mg2+, Ca2+, Sr2+, and Ba2+ cation. The ionic sizes estimated from the effective potentials are not pairwise additive, a feature in the frequently used primitive model for electrolytes. The effective potentials were used in Monte Carlo (MC) simulations with implicit water to calculate mean ion activity coefficients of LiCl, NaCl, KCl, MgCl2, CaCl2, SrCl2, and BaCl2. Predicted activities were compared with experimental ones in the electrolyte... (More)
The potential of mean force (PMF) acting between two simple ions surrounded by SPC/E water have been determined by molecular dynamics (MD) simulations using a spherical cavity approach. Such effective ion-ion potentials were obtained for Me-Me, Me-Cl-, and Cl--Cl- pairs, where Me is a Li+, Na+, K+, Mg2+, Ca2+, Sr2+, and Ba2+ cation. The ionic sizes estimated from the effective potentials are not pairwise additive, a feature in the frequently used primitive model for electrolytes. The effective potentials were used in Monte Carlo (MC) simulations with implicit water to calculate mean ion activity coefficients of LiCl, NaCl, KCl, MgCl2, CaCl2, SrCl2, and BaCl2. Predicted activities were compared with experimental ones in the electrolyte concentration range 0.1-1 M. A qualitative agreement for LiCl and a satisfactory agreement for NaCl were found, whereas the predictions for KCl by two K+ models were less coherent. In the case of alkaline earth metal ions, all experimental activities were successfully reproduced at c = 0.1 M. However, at higher concentrations, similar deviations occurred for all divalent cations, suggesting that the dependence of the permittivity on the salt concentration and the polarization deficiency arising from the ordering of water molecules in the ion hydration shells are important in such systems. (Less)
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type
Contribution to journal
publication status
published
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in
The Journal of Physical Chemistry Part B
volume
110
issue
22
pages
10878 - 10887
publisher
The American Chemical Society (ACS)
external identifiers
  • wos:000237954000040
  • scopus:33745433059
ISSN
1520-5207
DOI
10.1021/jp056871i
language
English
LU publication?
yes
id
43d6cef5-7d0d-4e5f-afcc-84554dc8db8e (old id 408296)
date added to LUP
2016-04-01 15:50:05
date last changed
2021-10-03 03:39:26
@article{43d6cef5-7d0d-4e5f-afcc-84554dc8db8e,
  abstract     = {The potential of mean force (PMF) acting between two simple ions surrounded by SPC/E water have been determined by molecular dynamics (MD) simulations using a spherical cavity approach. Such effective ion-ion potentials were obtained for Me-Me, Me-Cl-, and Cl--Cl- pairs, where Me is a Li+, Na+, K+, Mg2+, Ca2+, Sr2+, and Ba2+ cation. The ionic sizes estimated from the effective potentials are not pairwise additive, a feature in the frequently used primitive model for electrolytes. The effective potentials were used in Monte Carlo (MC) simulations with implicit water to calculate mean ion activity coefficients of LiCl, NaCl, KCl, MgCl2, CaCl2, SrCl2, and BaCl2. Predicted activities were compared with experimental ones in the electrolyte concentration range 0.1-1 M. A qualitative agreement for LiCl and a satisfactory agreement for NaCl were found, whereas the predictions for KCl by two K+ models were less coherent. In the case of alkaline earth metal ions, all experimental activities were successfully reproduced at c = 0.1 M. However, at higher concentrations, similar deviations occurred for all divalent cations, suggesting that the dependence of the permittivity on the salt concentration and the polarization deficiency arising from the ordering of water molecules in the ion hydration shells are important in such systems.},
  author       = {Gavryushov, Sergei and Linse, Per},
  issn         = {1520-5207},
  language     = {eng},
  number       = {22},
  pages        = {10878--10887},
  publisher    = {The American Chemical Society (ACS)},
  series       = {The Journal of Physical Chemistry Part B},
  title        = {Effective interaction potentials for alkali and alkaline earth metal ions in SPC/E water and prediction of mean ion activity coefficients},
  url          = {http://dx.doi.org/10.1021/jp056871i},
  doi          = {10.1021/jp056871i},
  volume       = {110},
  year         = {2006},
}