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Solvent Dependence of the Electronic Structure of I- and I-3(-)

Eriksson, Susanna K.; Josefsson, Ida; Ottosson, Niklas; Öhrwall, Gunnar LU ; Bjorneholm, Olle; Siegbahn, Hans; Hagfeldt, Anders; Odelius, Michael and Rensmo, Hakan (2014) In The Journal of Physical Chemistry Part B 118(11). p.3164-3174
Abstract
We present synchrotron-based I4d photoelectron spectroscopy experiments of solutions from LiI and LiI3 in water, ethanol, and acetonitrile. The experimentally determined solvent-induced binding energy shifts (SIBES) for the monatomic I- anion are compared to predictions from simple Born theory, PCM calculations, as well as multiconfigurational quantum chemical spectral calculations from geometries obtained through molecular dynamics of solvated clusters. We show that the SIBES for I- explicitly depend on the details of the hydrogen bonding configurations of the solvent to the I- and that static continuum models such as the Born model cannot capture the trends in the SIBES observed both in experiments and in higher-level calculations. To... (More)
We present synchrotron-based I4d photoelectron spectroscopy experiments of solutions from LiI and LiI3 in water, ethanol, and acetonitrile. The experimentally determined solvent-induced binding energy shifts (SIBES) for the monatomic I- anion are compared to predictions from simple Born theory, PCM calculations, as well as multiconfigurational quantum chemical spectral calculations from geometries obtained through molecular dynamics of solvated clusters. We show that the SIBES for I- explicitly depend on the details of the hydrogen bonding configurations of the solvent to the I- and that static continuum models such as the Born model cannot capture the trends in the SIBES observed both in experiments and in higher-level calculations. To extend the discussion to more complex polyatomic anions, we also performed experiments on I-3(-) and I-/I-3(-) mixtures in different solvents and the results are analyzed in the perspective of SIBES. The experimental SIBES values indicate that the solvation effects even for such similar anions as I- and I-3(-) can be rather different in nature. (Less)
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author
organization
publishing date
type
Contribution to journal
publication status
published
subject
in
The Journal of Physical Chemistry Part B
volume
118
issue
11
pages
3164 - 3174
publisher
The American Chemical Society
external identifiers
  • wos:000333381800039
  • scopus:84897846458
ISSN
1520-5207
DOI
10.1021/jp500533n
language
English
LU publication?
yes
id
31737b83-5821-4d94-ad8f-4fac584c3648 (old id 4407694)
date added to LUP
2014-04-29 09:31:16
date last changed
2017-10-01 04:19:37
@article{31737b83-5821-4d94-ad8f-4fac584c3648,
  abstract     = {We present synchrotron-based I4d photoelectron spectroscopy experiments of solutions from LiI and LiI3 in water, ethanol, and acetonitrile. The experimentally determined solvent-induced binding energy shifts (SIBES) for the monatomic I- anion are compared to predictions from simple Born theory, PCM calculations, as well as multiconfigurational quantum chemical spectral calculations from geometries obtained through molecular dynamics of solvated clusters. We show that the SIBES for I- explicitly depend on the details of the hydrogen bonding configurations of the solvent to the I- and that static continuum models such as the Born model cannot capture the trends in the SIBES observed both in experiments and in higher-level calculations. To extend the discussion to more complex polyatomic anions, we also performed experiments on I-3(-) and I-/I-3(-) mixtures in different solvents and the results are analyzed in the perspective of SIBES. The experimental SIBES values indicate that the solvation effects even for such similar anions as I- and I-3(-) can be rather different in nature.},
  author       = {Eriksson, Susanna K. and Josefsson, Ida and Ottosson, Niklas and Öhrwall, Gunnar and Bjorneholm, Olle and Siegbahn, Hans and Hagfeldt, Anders and Odelius, Michael and Rensmo, Hakan},
  issn         = {1520-5207},
  language     = {eng},
  number       = {11},
  pages        = {3164--3174},
  publisher    = {The American Chemical Society},
  series       = {The Journal of Physical Chemistry Part B},
  title        = {Solvent Dependence of the Electronic Structure of I- and I-3(-)},
  url          = {http://dx.doi.org/10.1021/jp500533n},
  volume       = {118},
  year         = {2014},
}