title: Solvent dependence of the electronic structure of I(-) and I3(-).
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 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.
authors.affiliation: Department of Chemistry-Ångström, Uppsala University , Box 523, SE-751 20 Uppsala, Sweden.
authors.forename: Susanna K
authors.initials: SK
authors.lastname: Eriksson
authors.forename: Ida
authors.initials: I
authors.lastname: Josefsson
authors.forename: Niklas
authors.initials: N
authors.lastname: Ottosson
authors.forename: Gunnar
authors.initials: G
authors.lastname: Öhrwall
authors.forename: Olle
authors.initials: O
authors.lastname: Björneholm
authors.forename: Hans
authors.initials: H
authors.lastname: Siegbahn
authors.forename: Anders
authors.initials: A
authors.lastname: Hagfeldt
authors.forename: Michael
authors.initials: M
authors.lastname: Odelius
authors.forename: Håkan
authors.initials: H
authors.lastname: Rensmo