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Photo Mikael Lund

Mikael Lund

Professor

Photo Mikael Lund

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

Author

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

Summary, in English

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.

Department/s

  • Computational Chemistry
  • eSSENCE: The e-Science Collaboration

Publishing year

2010

Language

English

Pages

10843-10852

Publication/Series

The Journal of Physical Chemistry Part B

Volume

114

Issue

33

Document type

Journal article

Publisher

The American Chemical Society (ACS)

Topic

  • Theoretical Chemistry (including Computational Chemistry)

Status

Published

ISBN/ISSN/Other

  • ISSN: 1520-5207