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Solvation and ion-pairing properties of the aqueous sulfate anion: explicit versus effective electronic polarization

Pegado, Luis; Marsalek, Ondrej; Jungwirth, Pavel and Wernersson, Erik LU (2012) In Physical Chemistry Chemical Physics 14(29). p.10248-10257
Abstract
We assessed the relative merits of two approaches for including polarization effects in classical force fields for the sulfate anion. One of the approaches is the explicit shell model for atomic polarization and the other is an implicit dielectric continuum representation of the electronic polarization, wherein the polarizability density is spatially uniform. Both the solvation and ion association properties of sulfate were considered. We carried out an ab initio molecular dynamics simulation for a single sulfate anion in aqueous solution to obtain a benchmark for the solvation structure. For the ion-pairing properties, the models were compared to experimental thermodynamic data through Kirkwood-Buff theory, which relates the integrals of... (More)
We assessed the relative merits of two approaches for including polarization effects in classical force fields for the sulfate anion. One of the approaches is the explicit shell model for atomic polarization and the other is an implicit dielectric continuum representation of the electronic polarization, wherein the polarizability density is spatially uniform. Both the solvation and ion association properties of sulfate were considered. We carried out an ab initio molecular dynamics simulation for a single sulfate anion in aqueous solution to obtain a benchmark for the solvation structure. For the ion-pairing properties, the models were compared to experimental thermodynamic data through Kirkwood-Buff theory, which relates the integrals of the pair correlation functions to measurable properties. While deficiencies were found for both of the approaches, the continuum polarization model was not systematically worse than the shell model. The shell model was found to give a more structured solution than the continuum polarization model, both with respect to solvation and ion pairing. (Less)
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author
organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Physical Chemistry Chemical Physics
volume
14
issue
29
pages
10248 - 10257
publisher
Royal Society of Chemistry
external identifiers
  • wos:000305965200022
  • scopus:84863652661
ISSN
1463-9084
DOI
10.1039/c2cp40711f
language
English
LU publication?
yes
id
e209b8b7-f5bc-40f6-9cb8-123e2e9bd33c (old id 3008047)
date added to LUP
2012-08-21 08:59:33
date last changed
2017-02-26 03:59:02
@article{e209b8b7-f5bc-40f6-9cb8-123e2e9bd33c,
  abstract     = {We assessed the relative merits of two approaches for including polarization effects in classical force fields for the sulfate anion. One of the approaches is the explicit shell model for atomic polarization and the other is an implicit dielectric continuum representation of the electronic polarization, wherein the polarizability density is spatially uniform. Both the solvation and ion association properties of sulfate were considered. We carried out an ab initio molecular dynamics simulation for a single sulfate anion in aqueous solution to obtain a benchmark for the solvation structure. For the ion-pairing properties, the models were compared to experimental thermodynamic data through Kirkwood-Buff theory, which relates the integrals of the pair correlation functions to measurable properties. While deficiencies were found for both of the approaches, the continuum polarization model was not systematically worse than the shell model. The shell model was found to give a more structured solution than the continuum polarization model, both with respect to solvation and ion pairing.},
  author       = {Pegado, Luis and Marsalek, Ondrej and Jungwirth, Pavel and Wernersson, Erik},
  issn         = {1463-9084},
  language     = {eng},
  number       = {29},
  pages        = {10248--10257},
  publisher    = {Royal Society of Chemistry},
  series       = {Physical Chemistry Chemical Physics},
  title        = {Solvation and ion-pairing properties of the aqueous sulfate anion: explicit versus effective electronic polarization},
  url          = {http://dx.doi.org/10.1039/c2cp40711f},
  volume       = {14},
  year         = {2012},
}