Dielectric Interpretation of Specificity of Ion Pairing in Water
Lund, Mikael LU
; Jagoda-Cwiklik, Barbara
; Woodward, Clifford E.
; Vácha, Robert
and Jungwirth, Pavel
(2010)
In The Journal of Physical Chemistry Letters
1(1).
p.300-303
- Abstract
- We present a dielectric continuum model that, at a semiquantitative level, explains why ion pair formation in water is favored by like-sized ions over unlike-sized pairs. Using both classical and ab initio continuum approaches, we show that the now well-established empirical rule, the so-called “law of matching water affinities”, can be rationalized in terms of ion solvation. Namely, pairing of differently sized ions is weakened due to a shadowing effect where the larger ion shields the smaller ion from the solvent. It is shown that this empirical law ceases to be valid for less polar solvents where strong ion−ion coulomb interactions dominate the pairing free energy. The presented model demonstrates that certain ion-specific effects, such... (More)
- We present a dielectric continuum model that, at a semiquantitative level, explains why ion pair formation in water is favored by like-sized ions over unlike-sized pairs. Using both classical and ab initio continuum approaches, we show that the now well-established empirical rule, the so-called “law of matching water affinities”, can be rationalized in terms of ion solvation. Namely, pairing of differently sized ions is weakened due to a shadowing effect where the larger ion shields the smaller ion from the solvent. It is shown that this empirical law ceases to be valid for less polar solvents where strong ion−ion coulomb interactions dominate the pairing free energy. The presented model demonstrates that certain ion-specific effects, such as those connected with the Hofmeister series, can be qualitatively captured by classical continuum electrostatics, although a fully quantitative description would require explicit molecular treatment of the solvent. (Less)
Please use this url to cite or link to this publication:
https://lup.lub.lu.se/record/7763578
- author
- Lund, Mikael
LU
; Jagoda-Cwiklik, Barbara
; Woodward, Clifford E.
; Vácha, Robert
and Jungwirth, Pavel
- organization
- publishing date
- 2010
- type
- Contribution to journal
- publication status
- published
- subject
- keywords
- ion pairing, Hofmeister series, dielectric continuum, ion specificity, primitive model of electrolytes, solvation, electrolyte solutions
- in
- The Journal of Physical Chemistry Letters
- volume
- 1
- issue
- 1
- pages
- 300 - 303
- publisher
- The American Chemical Society (ACS)
- external identifiers
-
- wos:000276905600064
- scopus:84962376834
- ISSN
- 1948-7185
- DOI
- 10.1021/jz900151f
- language
- English
- LU publication?
- yes
- additional info
- The information about affiliations in this record was updated in December 2015. The record was previously connected to the following departments: Theoretical Chemistry (S) (011001039)
- id
- 82a7d83e-e90d-45e4-b5f4-8ac49f2c8cf6 (old id 7763578)
- date added to LUP
- 2016-04-01 13:20:37
- date last changed
- 2023-04-06 04:40:30
@article{82a7d83e-e90d-45e4-b5f4-8ac49f2c8cf6,
abstract = {{We present a dielectric continuum model that, at a semiquantitative level, explains why ion pair formation in water is favored by like-sized ions over unlike-sized pairs. Using both classical and ab initio continuum approaches, we show that the now well-established empirical rule, the so-called “law of matching water affinities”, can be rationalized in terms of ion solvation. Namely, pairing of differently sized ions is weakened due to a shadowing effect where the larger ion shields the smaller ion from the solvent. It is shown that this empirical law ceases to be valid for less polar solvents where strong ion−ion coulomb interactions dominate the pairing free energy. The presented model demonstrates that certain ion-specific effects, such as those connected with the Hofmeister series, can be qualitatively captured by classical continuum electrostatics, although a fully quantitative description would require explicit molecular treatment of the solvent.}},
author = {{Lund, Mikael and Jagoda-Cwiklik, Barbara and Woodward, Clifford E. and Vácha, Robert and Jungwirth, Pavel}},
issn = {{1948-7185}},
keywords = {{ion pairing; Hofmeister series; dielectric continuum; ion specificity; primitive model of electrolytes; solvation; electrolyte solutions}},
language = {{eng}},
number = {{1}},
pages = {{300--303}},
publisher = {{The American Chemical Society (ACS)}},
series = {{The Journal of Physical Chemistry Letters}},
title = {{Dielectric Interpretation of Specificity of Ion Pairing in Water}},
url = {{http://dx.doi.org/10.1021/jz900151f}},
doi = {{10.1021/jz900151f}},
volume = {{1}},
year = {{2010}},
}