Reversal of Hofmeister Ordering for Pairing of NH4+ vs Alkylated Ammonium Cations with Halide Anions in Water
(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)
Please use this url to cite or link to this publication:
https://lup.lub.lu.se/record/1673663
- author
- Heyda, Jan ; Lund, Mikael LU ; Oncak, Milan ; Slavicek, Petr and Jungwirth, Pavel
- organization
- publishing date
- 2010
- 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 (ACS)
- external identifiers
-
- wos:000280962100019
- scopus:77955900022
- pmid:20677759
- ISSN
- 1520-5207
- DOI
- 10.1021/jp101393k
- 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
- 03ba2259-6323-48de-b8b1-91ee22453947 (old id 1673663)
- date added to LUP
- 2016-04-01 14:45:03
- date last changed
- 2023-04-07 03:20:25
@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 (ACS)}}, 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}}, doi = {{10.1021/jp101393k}}, volume = {{114}}, year = {{2010}}, }