PhD Thesis: Structure and dynamics in solution – the core electron perspective
Thursday 15 October 2015
to 13:00 at
Ida Josefsson (Stockholm University, Department of Physics)
This thesis is based on theoretical studies of the molecular and electronic structure of solvated ions and molecules. Very
detailed information of the system can be obtained from theoretical calculations, but a realistic model is dependent on
an accurate computational method. Accurate calculations of core level electronic spectra, and evaluation of the modeling
against experiments, are central parts of this work. The main tools used for characterization of the systems are high-level
quantum chemistry and molecular dynamics simulations.
Molecular components in solutions are involved in many key processes converting sunlight into chemical or electrical
energy. Transition metal complexes, with their pronounced absorption in the visible light region of the electromagnetic
spectrum, are core components in various energy conversion applications, and the iodide/triiodide redox couple is a
commonly used electrolyte. The local structure of the electronic valence in transition metal complexes and the details of
the solvation mechanisms of electrolyte solutions are investigated through the combination of computational modeling and
core level spectroscopy. The studies of model systems show that interactions between the solute and solvent are important
for the electronic structure, and knowledge of the details in model systems studied can be relevant for energy conversion
applications. Furthermore, high-level quantum chemistry has been applied for interpreting time-resolved spectra, where
the electronic structure of a metal complex is followed during a photoinduced chemical reaction in solution.
With advanced modeling in combination with recent experimental developments, more complex problems than
previously addressed can be dissected.