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Many-body polarization, a cause of asymmetric solvation of ions and quadrupoles

Öhrn, Anders LU and Karlström, Gunnar LU (2007) In Journal of Chemical Theory and Computation 3(6). p.1993-2001
Abstract
Three models are used to study the effect of many-body polarization in the solvation of non-dipolar molecules and ions in water. Two of the models are very simplified and are used to show a number of basic principles of correlation of solvent degrees of freedom and asymmetric solvent structures. These principles are used to interpret results from the third model: an accurate simulation of para-benzoquinone (PBQ) in aqueous solution with a combined quantum chemical statistical mechanical solvent model with an explicit solvent. It is found that nonzero polarizability of PBQ introduces correlation in the solvent degrees of freedom through the many-body nature of the polarization. The fluctuating electric field from the solvent on the solute... (More)
Three models are used to study the effect of many-body polarization in the solvation of non-dipolar molecules and ions in water. Two of the models are very simplified and are used to show a number of basic principles of correlation of solvent degrees of freedom and asymmetric solvent structures. These principles are used to interpret results from the third model: an accurate simulation of para-benzoquinone (PBQ) in aqueous solution with a combined quantum chemical statistical mechanical solvent model with an explicit solvent. It is found that nonzero polarizability of PBQ introduces correlation in the solvent degrees of freedom through the many-body nature of the polarization. The fluctuating electric field from the solvent on the solute increases in magnitude with the correlation. Solvent effects are hence modified. This correlation is not described within the mean-field approximation. In practice, the correlation will show up as an increased probability for asymmetric solvation of the molecule. (Less)
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author
organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Journal of Chemical Theory and Computation
volume
3
issue
6
pages
1993 - 2001
publisher
The American Chemical Society
external identifiers
  • wos:000251024200010
  • scopus:36749099534
ISSN
1549-9618
DOI
10.1021/ct700022b
language
English
LU publication?
yes
id
547bd90e-ffb2-44fa-8346-5d993e40de2a (old id 969065)
date added to LUP
2008-01-30 07:37:38
date last changed
2017-01-01 05:02:01
@article{547bd90e-ffb2-44fa-8346-5d993e40de2a,
  abstract     = {Three models are used to study the effect of many-body polarization in the solvation of non-dipolar molecules and ions in water. Two of the models are very simplified and are used to show a number of basic principles of correlation of solvent degrees of freedom and asymmetric solvent structures. These principles are used to interpret results from the third model: an accurate simulation of para-benzoquinone (PBQ) in aqueous solution with a combined quantum chemical statistical mechanical solvent model with an explicit solvent. It is found that nonzero polarizability of PBQ introduces correlation in the solvent degrees of freedom through the many-body nature of the polarization. The fluctuating electric field from the solvent on the solute increases in magnitude with the correlation. Solvent effects are hence modified. This correlation is not described within the mean-field approximation. In practice, the correlation will show up as an increased probability for asymmetric solvation of the molecule.},
  author       = {Öhrn, Anders and Karlström, Gunnar},
  issn         = {1549-9618},
  language     = {eng},
  number       = {6},
  pages        = {1993--2001},
  publisher    = {The American Chemical Society},
  series       = {Journal of Chemical Theory and Computation},
  title        = {Many-body polarization, a cause of asymmetric solvation of ions and quadrupoles},
  url          = {http://dx.doi.org/10.1021/ct700022b},
  volume       = {3},
  year         = {2007},
}