Collective hydrogen-bond dynamics dictates the electronic structure of aqueous I-3(-)
Författare
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.
Avdelning/ar
Publiceringsår
2013
Språk
Engelska
Sidor
20189-20196
Publikation/Tidskrift/Serie
Physical Chemistry Chemical Physics
Volym
15
Issue
46
Dokumenttyp
Artikel i tidskrift
Förlag
Royal Society of Chemistry
Ämne
- Natural Sciences
- Physical Sciences
Status
Published
ISBN/ISSN/Övrigt
- ISSN: 1463-9084