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Polarization deficiency and excess free energy of ion hydration in electric fields

Gavryushov, Sergei LU and Linse, Per LU (2003) In The Journal of Physical Chemistry Part B 107(29). p.7135-7142
Abstract
Polarization deficiency and excess ion hydration free energy at an electric field E (ion hydration free energy at the field E subtracted by the ion hydration free energy at zero field) of hydrated calcium, sodium, and chlori

e ions have been determined by Monte Carlo simulations. A spherical cell containing either one ion and molecular water or only molecular water subjected to an external electrical field was used. The permittivity of pure water decreases as E is increased, in quantitative agreement with previous simulation studies and the Booth theory. The excess ion hydration free energy depends quadratically on E up to ca. 2.5.10(8) V/m, whereas it becomes linear in E at higher field due to dielectric saturation. The values of... (More)
Polarization deficiency and excess ion hydration free energy at an electric field E (ion hydration free energy at the field E subtracted by the ion hydration free energy at zero field) of hydrated calcium, sodium, and chlori

e ions have been determined by Monte Carlo simulations. A spherical cell containing either one ion and molecular water or only molecular water subjected to an external electrical field was used. The permittivity of pure water decreases as E is increased, in quantitative agreement with previous simulation studies and the Booth theory. The excess ion hydration free energy depends quadratically on E up to ca. 2.5.10(8) V/m, whereas it becomes linear in E at higher field due to dielectric saturation. The values of the excess ion hydration free energies are in quantitative agreement with measured dependencies of the relative permittivity of electrolyte solution upon the ion concentration. A primitive polarization model of electrolyte solution near charged interfaces is proposed. The use of this model leads to an additional effective repulsive force acting on hydrated ions near charged surfaces and significantly affects the distribution of calcium ions near such surfaces. (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
107
issue
29
pages
7135 - 7142
publisher
The American Chemical Society
external identifiers
  • wos:000184242600030
  • scopus:0042705202
ISSN
1520-5207
DOI
10.1021/jp030035w
language
English
LU publication?
yes
id
428e43a7-797a-4b0b-b88c-b4cd083d1514 (old id 122003)
date added to LUP
2007-07-11 12:02:40
date last changed
2017-02-12 04:11:48
@article{428e43a7-797a-4b0b-b88c-b4cd083d1514,
  abstract     = {Polarization deficiency and excess ion hydration free energy at an electric field E (ion hydration free energy at the field E subtracted by the ion hydration free energy at zero field) of hydrated calcium, sodium, and chlori<br/><br>
e ions have been determined by Monte Carlo simulations. A spherical cell containing either one ion and molecular water or only molecular water subjected to an external electrical field was used. The permittivity of pure water decreases as E is increased, in quantitative agreement with previous simulation studies and the Booth theory. The excess ion hydration free energy depends quadratically on E up to ca. 2.5.10(8) V/m, whereas it becomes linear in E at higher field due to dielectric saturation. The values of the excess ion hydration free energies are in quantitative agreement with measured dependencies of the relative permittivity of electrolyte solution upon the ion concentration. A primitive polarization model of electrolyte solution near charged interfaces is proposed. The use of this model leads to an additional effective repulsive force acting on hydrated ions near charged surfaces and significantly affects the distribution of calcium ions near such surfaces.},
  author       = {Gavryushov, Sergei and Linse, Per},
  issn         = {1520-5207},
  language     = {eng},
  number       = {29},
  pages        = {7135--7142},
  publisher    = {The American Chemical Society},
  series       = {The Journal of Physical Chemistry Part B},
  title        = {Polarization deficiency and excess free energy of ion hydration in electric fields},
  url          = {http://dx.doi.org/10.1021/jp030035w},
  volume       = {107},
  year         = {2003},
}