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doi:10.1016/j.cplett.2005.05.084 
Copyright © 2005 Elsevier B.V. All rights reserved.
Effect of bromide on the interfacial structure of aqueous tetrabutylammonium iodide: Photoelectron spectroscopy and molecular dynamics simulations
Bernd Wintera, 
, 
, Ramona Webera, Ingolf V. Hertela, Manfred Faubelb, Luboš Vrbkac and Pavel Jungwirthc, ,
Received 1 March 2005;
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Abstract
Solvation of surface-active tetrabutylammonium iodide (TBAI) in liquid water and in sodium bromide aqueous solution was investigated by VUV photoelectron spectroscopy and by molecular dynamics simulations. The observed signal intensity changes in the photoemission spectra are consistent with the varying propensities of the different ions for the solution interface. While the cations are surface-bound due to hydrophobic interactions, the anions are driven to the vacuum/solution interface by their large polarizability and size. Iodide is more polarizable, and hence more surface-active than bromide, which explains the relatively small decrease of the iodide photoemission signal when TBAI is dissolved in bromide solution.
