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

Jan Heyda; Mikael Lund; Milan Oncak; Petr Slavicek; Pavel Jungwirth

doi:10.1021/jp101393k

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

Jan Heyda, Mikael Lund, Milan Oncak, Petr Slavicek, Pavel Jungwirth

Research output: Contribution to journal › Article › peer-review

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.

Original language	English
Pages (from-to)	10843-10852
Journal	The Journal of Physical Chemistry Part B
Volume	114
Issue number	33
DOIs	https://doi.org/10.1021/jp101393k
Publication status	Published - 2010

Bibliographical note

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)

Subject classification (UKÄ)

Theoretical Chemistry (including Computational Chemistry)

Access to Document

10.1021/jp101393k

Cite this

@article{03ba2259632348deb8b191ee22453947,

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

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 = "Jan Heyda and Mikael Lund and Milan Oncak and Petr Slavicek and Pavel Jungwirth",

note = "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)",

year = "2010",

doi = "10.1021/jp101393k",

language = "English",

volume = "114",

pages = "10843--10852",

journal = "The Journal of Physical Chemistry Part B",

issn = "1520-5207",

publisher = "The American Chemical Society (ACS)",

number = "33",

}

TY - JOUR

T1 - Reversal of Hofmeister Ordering for Pairing of NH4+ vs Alkylated Ammonium Cations with Halide Anions in Water

AU - Heyda, Jan

AU - Lund, Mikael

AU - Oncak, Milan

AU - Slavicek, Petr

AU - Jungwirth, Pavel

N1 - 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)

PY - 2010

Y1 - 2010

N2 - 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.

AB - 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.

UR - https://www.scopus.com/pages/publications/77955900022

U2 - 10.1021/jp101393k

DO - 10.1021/jp101393k

M3 - Article

C2 - 20677759

SN - 1520-5207

VL - 114

SP - 10843

EP - 10852

JO - The Journal of Physical Chemistry Part B

JF - The Journal of Physical Chemistry Part B

IS - 33

ER -

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

Abstract

Bibliographical note

Subject classification (UKÄ)

Access to Document

Other files and links

Fingerprint

Cite this