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

Josefsson, Ida; Eriksson, Susanna K.; Ottosson, Niklas; Öhrwall, Gunnar LU ; Siegbahn, Hans; Hagfeldt, Anders; Rensmo, Hakan; Bjorneholm, Olle and Odelius, Michael (2013) In Physical Chemistry Chemical Physics 15(46). p.20189-20196
Abstract
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... (More)
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. (Less)
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author
organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Physical Chemistry Chemical Physics
volume
15
issue
46
pages
20189 - 20196
publisher
Royal Society of Chemistry
external identifiers
  • wos:000326747200028
  • scopus:84888356437
ISSN
1463-9084
DOI
10.1039/c3cp52866a
language
English
LU publication?
yes
id
ab751dc0-35f8-4b99-9eb9-cb009136704c (old id 4204187)
date added to LUP
2014-01-13 11:31:10
date last changed
2019-10-23 03:12:33
@article{ab751dc0-35f8-4b99-9eb9-cb009136704c,
  abstract     = {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.},
  author       = {Josefsson, Ida and Eriksson, Susanna K. and Ottosson, Niklas and Öhrwall, Gunnar and Siegbahn, Hans and Hagfeldt, Anders and Rensmo, Hakan and Bjorneholm, Olle and Odelius, Michael},
  issn         = {1463-9084},
  language     = {eng},
  number       = {46},
  pages        = {20189--20196},
  publisher    = {Royal Society of Chemistry},
  series       = {Physical Chemistry Chemical Physics},
  title        = {Collective hydrogen-bond dynamics dictates the electronic structure of aqueous I-3(-)},
  url          = {http://dx.doi.org/10.1039/c3cp52866a},
  volume       = {15},
  year         = {2013},
}