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Reversal of Hofmeister Ordering for Pairing of NH4+ vs Alkylated Ammonium Cations with Halide Anions in Water

Heyda, Jan; Lund, Mikael LU ; Oncak, Milan; Slavicek, Petr and Jungwirth, Pavel (2010) In The Journal of Physical Chemistry Part B 114(33). p.10843-10852
Abstract
Pairing of halide anions with ammonium, as well as with trialkylated and tetraalkylated ammonium cations in water, is investigated by molecular dynamics simulations, which are verified by ab initio calculations and experimental excess chemical potentials. We find that ammonium prefers to pair with smaller halides over the larger ones, while the order is reversed for tetraalkylated ammonium cations. Trialkylated ammonium cations exhibit an intermediate behavior, with the acidic hydrogen preferring smaller anions and alkyl chains interacting attractively with larger halides. This Hofmeister reversal of anionic ordering upon tetraalkylation of the ammonium cation is robustly predicted by both nonpolarizable and polarizable force fields and... (More)
Pairing of halide anions with ammonium, as well as with trialkylated and tetraalkylated ammonium cations in water, is investigated by molecular dynamics simulations, which are verified by ab initio calculations and experimental excess chemical potentials. We find that ammonium prefers to pair with smaller halides over the larger ones, while the order is reversed for tetraalkylated ammonium cations. Trialkylated ammonium cations exhibit an intermediate behavior, with the acidic hydrogen preferring smaller anions and alkyl chains interacting attractively with larger halides. This Hofmeister reversal of anionic ordering upon tetraalkylation of the ammonium cation is robustly predicted by both nonpolarizable and polarizable force fields and supported by experimental evidence. (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
114
issue
33
pages
10843 - 10852
publisher
The American Chemical Society
external identifiers
  • wos:000280962100019
  • scopus:77955900022
ISSN
1520-5207
DOI
10.1021/jp101393k
language
English
LU publication?
yes
id
03ba2259-6323-48de-b8b1-91ee22453947 (old id 1673663)
date added to LUP
2010-09-23 09:15:19
date last changed
2018-05-29 11:11:32
@article{03ba2259-6323-48de-b8b1-91ee22453947,
  abstract     = {Pairing of halide anions with ammonium, as well as with trialkylated and tetraalkylated ammonium cations in water, is investigated by molecular dynamics simulations, which are verified by ab initio calculations and experimental excess chemical potentials. We find that ammonium prefers to pair with smaller halides over the larger ones, while the order is reversed for tetraalkylated ammonium cations. Trialkylated ammonium cations exhibit an intermediate behavior, with the acidic hydrogen preferring smaller anions and alkyl chains interacting attractively with larger halides. This Hofmeister reversal of anionic ordering upon tetraalkylation of the ammonium cation is robustly predicted by both nonpolarizable and polarizable force fields and supported by experimental evidence.},
  author       = {Heyda, Jan and Lund, Mikael and Oncak, Milan and Slavicek, Petr and Jungwirth, Pavel},
  issn         = {1520-5207},
  language     = {eng},
  number       = {33},
  pages        = {10843--10852},
  publisher    = {The American Chemical Society},
  series       = {The Journal of Physical Chemistry Part B},
  title        = {Reversal of Hofmeister Ordering for Pairing of NH4+ vs Alkylated Ammonium Cations with Halide Anions in Water},
  url          = {http://dx.doi.org/10.1021/jp101393k},
  volume       = {114},
  year         = {2010},
}