Australian Journal of Chemistry Australian Journal of Chemistry Society
An international journal for chemical science

Counter-Ion Effects and Interfacial Properties of Aqueous Tetrabutylammonium Halide Solutions

Luboš Vrbka A and Pavel Jungwirth A B
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A Institute of Organic Chemistry and Biochemistry, Academy of Sciences of the Czech Republic, and Center for Complex Molecular Systems and Biomolecules, Flemingovo nam. 2, 16610 Prague 6, Czech Republic.

B Corresponding author. Email:

Australian Journal of Chemistry 57(12) 1211-1217
Submitted: 12 May 2004  Accepted: 17 August 2004   Published: 8 December 2004


Aqueous solvation of tetrabutylammonium fluoride and iodide was investigated by means of molecular dynamics simulations in extended slab geometry. The varying propensities of the individual ions for the air/water interface were quantified and analyzed in terms of hydrophobic, polarization, and ion–ion interactions. While the cations behave as standard ionic surfactants, the surface behaviour of the halide counter ions strongly depends on the ionic size and polarizability—iodide is surface active, while fluoride is repelled from the interface. The counter-ion effects at different concentrations on the density and charge profiles across the aqueous slab are discussed in detail.


This work has been completed within the framework of research project Z4 055 905. We thank the METAcenter Project—Supercomputer Center Brno, Westbohemian Supercomputer Center, and Supercomputer Center Prague for providing computer facilities for our work. Support for the Center of Complex Molecular Systems and Biomolecules from the Czech Ministry of Education (grant LN00A032) and from the USA-NSF (grant CHE–0209719) is gratefully acknowledged.


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