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Collective hydrogen-bond dynamics dictates the electronic structure of aqueous I-3(-)

På svenska

Author

  • Ida Josefsson
  • Susanna K. Eriksson
  • Niklas Ottosson
  • Gunnar Öhrwall
  • Hans Siegbahn
  • Anders Hagfeldt
  • Hakan Rensmo
  • Olle Bjorneholm
  • Michael Odelius

Summary, in English

The molecular and electronic structures of aqueous I-3 and I ions have been investigated through ab initio molecular dynamics (MD) simulations and photoelectron (PE) spectroscopy of the iodine 4d core levels. Against the background of the theoretical simulations, data from our I4d PE measurements are shown to contain evidence of coupled solute-solvent dynamics. The MD simulations reveal large amplitude fluctuations in the I-I distances, which couple to the collective rearrangement of the hydrogen bonding network around the I-3(-) ion. Due to the high polarizability of the I-3(-) ion, the asymmetric I-I vibration reaches partially dissociated configurations, for which the electronic structure resembles that of I-2 + I-. The charge localization in the I-3(-) ion is found to be moderated by hydrogen-bonding. As seen in the PE spectrum, these soft molecular vibrations are important for the electronic properties of the I-3(-) ion in solution and may play an important role in its electrochemical function.

Department/s

Publishing year

2013

Language

English

Pages

20189-20196

Publication/Series

Physical Chemistry Chemical Physics

Volume

15

Issue

46

Document type

Journal article

Publisher

Royal Society of Chemistry

Topic

  • Natural Sciences
  • Physical Sciences

Status

Published

ISBN/ISSN/Other

  • ISSN: 1463-9084