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Solvent Dependence of the Electronic Structure of I- and I-3(-)
Stockholm University, Faculty of Science, Department of Physics.
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2014 (English)In: Journal of Physical Chemistry B, ISSN 1520-6106, E-ISSN 1520-5207, Vol. 118, no 11, 3164-3174 p.Article in journal (Refereed) Published
Abstract [en]

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.

Place, publisher, year, edition, pages
2014. Vol. 118, no 11, 3164-3174 p.
National Category
Physical Sciences
Research subject
Physics
Identifiers
URN: urn:nbn:se:su:diva-102957DOI: 10.1021/jp500533nISI: 000333381800039OAI: oai:DiVA.org:su-102957DiVA: diva2:714862
Note

AuthorCount:9;

Available from: 2014-04-29 Created: 2014-04-25 Last updated: 2017-12-05Bibliographically approved
In thesis
1. Structure and dynamics in solution – the core electron perspective
Open this publication in new window or tab >>Structure and dynamics in solution – the core electron perspective
2015 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

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.

Place, publisher, year, edition, pages
Stockholm: Department of Physics, Stockholm University, 2015. 64 p.
Keyword
quantum chemistry, RASSCF, molecular dynamics, x-ray spectroscopy, electrolyte solutions
National Category
Natural Sciences
Research subject
Physics
Identifiers
urn:nbn:se:su:diva-119838 (URN)978-91-7649-258-1 (ISBN)
Public defence
2015-10-15, sal FB42, AlbaNova universitetscentrum, Roslagstullsbacken 21, Stockholm, 10:00 (English)
Opponent
Supervisors
Note

At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 3: Submitted. Paper 8: Manuscript.

Available from: 2015-09-23 Created: 2015-08-26 Last updated: 2015-09-11Bibliographically approved

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