Surface Behavior of Hydrated Guanidinium and Ammonium Ions: A Comparative Study by Photoelectron Spectroscopy and Molecular Dynamics

Josephina Werner, Erik Wernersson, Victor Ekholm, Niklas Ottosson, Gunnar Öhrwall, Jan Heyda, Ingmar Persson, Johan Soderstrom, Pavel Jungwirth, Olle Bjorneholm

Research output: Contribution to journalArticlepeer-review

Abstract

Through the combination of surface sensitive photoelectron spectroscopy and molecular dynamics simulation, the relative surface propensities of guanidinium and ammonium ions in aqueous solution are characterized. The fact that the N Is binding energies differ between these two species was exploited to monitor their relative surface concentration through their respective photoemission intensities. Aqueous solutions of ammonium and guanidinium chloride, and mixtures of these salts, have been studied in a wide concentration range, and it is found that the guanidinium ion has a greater propensity to reside at the aqueous surface than the ammonium ion. A large portion of the relative excess of guanidinium ions in the surface region of the mixed solutions can be explained by replacement of ammonium ions by guanidinium ions in the surface region in combination with a strong salting-out effect of guanidinium by ammonium ions at increased concentrations. This interpretation is supported by molecular dynamics simulations, which reproduce the experimental trends very well. The simulations suggest that the relatively higher surface propensity of guanidinium compared with ammonium ions is due to the ease of dehydration of the faces of the almost planar guanidinium ion, which allows it to approach the water-vapor interface oriented parallel to it.
Original languageEnglish
Pages (from-to)7119-7127
JournalThe Journal of Physical Chemistry Part B
Volume118
Issue number25
DOIs
Publication statusPublished - 2014

Subject classification (UKÄ)

  • Physical Sciences
  • Natural Sciences

Fingerprint

Dive into the research topics of 'Surface Behavior of Hydrated Guanidinium and Ammonium Ions: A Comparative Study by Photoelectron Spectroscopy and Molecular Dynamics'. Together they form a unique fingerprint.

Cite this