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

Summary, in English

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: Susanna K. Eriksson; Ida Josefsson; Niklas Ottosson; Gunnar Öhrwall; Olle Bjorneholm; Hans Siegbahn; Anders Hagfeldt; Michael Odelius; Hakan Rensmo
• Department/s: MAX IV Laboratory
• Publishing year: 2014
• Language: English
• Pages: 3164-3174
• Publication/Series: The Journal of Physical Chemistry Part B
• Volume: 118
• Issue: 11
• Links: http://dx.doi.org/10.1021/jp500533n
• Document type: Journal article
• Publisher: The American Chemical Society (ACS)
• Topic: Physical Sciences; Natural Sciences
• Status: Published
• ISBN/ISSN/Other: ISSN: 1520-5207