Solvent‐Dependent Structure of the I3− Ion Derived from Photoelectron Spectroscopy and Ab Initio Molecular Dynamics Simulations. Issue 10 (28th January 2015)

• Record Type: Journal Article
• Authors: Jena, Naresh K.; Josefsson, Ida; Eriksson, Susanna K.; Hagfeldt, Anders; Siegbahn, Hans; Björneholm, Olle; Rensmo, Håkan; Odelius, Michael
• Is Part Of: Chemistry. Volume 21:Issue 10(2015)
• Page Start: 4049
• Page End: 4055
• Publication Date: 2015-01-28
• Subjects: ab initio calculations -- hydrogen bonds -- molecular dynamics -- photoelectron spectroscopy -- solvent effects; Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.201405549
• Languages: English
• ISSNs: 0947-6539

Abstract

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. Abstract : Finding common ground : A combination of ab initio molecular dynamics (MD) and X‐ray photoelectron spectroscopy (XPS) is used to disentangle the solution structure of I3 − in different solvents. In unravelling the solvent‐induced symmetry breaking of this ion, structural and electronic information obtained from theory provides interesting correlations with experimental results.