title: Solvent-dependent structure of the I3(-) ion derived from photoelectron spectroscopy and ab initio molecular dynamics simulations.
abstract: Ab initio molecular dynamics (MD) simulations of the solvation of LiI3 in four different solvents (water, methanol, ethanol, and acetonitrile) are employed to investigate the molecular and electronic structure of the I3(-) ion in relation to X-ray photoelectron spectroscopy (XPS). Simulations show that hydrogen-bond rearrangement in the solvation shell is coupled to intramolecular bond-length asymmetry in the I3(-) ion. By a combination of charge analysis and I 4 d core-level XPS measurements, the mechanism of the solvent-induced distortions has been studied, and it has been concluded that charge localization mediates intermolecular interactions and intramolecular distortion. The approach involving a synergistic combination of theory and experiment probes the solvent-dependent structure of the I3(-) ion, and the geometric structure has been correlated with the electronic structure.
authors: Department of Physics, Stockholm University, AlbaNova University Center, Roslagstullsbacken 21, 106 91 Stockholm (Sweden).
authors: Naresh K
authors: NK
authors: Jena
authors: Ida
authors: I
authors: Josefsson
authors: Susanna K
authors: SK
authors: Eriksson
authors: Anders
authors: A
authors: Hagfeldt
authors: Hans
authors: H
authors: Siegbahn
authors: Olle
authors: O
authors: Björneholm
authors: Håkan
authors: H
authors: Rensmo
authors: Michael
authors: M
authors: Odelius
keywords: ab initio calculations; hydrogen bonds; molecular dynamics; photoelectron spectroscopy; solvent effects