Solvent Dependence of the Electronic Structure of I– and I3–
2014
Eriksson, Susanna K. | Josefsson, Ida | Ottosson, Niklas | Öhrwall, Gunnar | Björneholm, O. (Olle) | Siegbahn, Hans | Hagfeldt, Anders | Odelius, Michael | Rensmo, Håkan
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 I₃– and I–/I₃– 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 I₃– can be rather different in nature.
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