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Collective hydrogen-bond dynamics dictates the electronic structure of aqueous I-3(-)
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Physical Chemistry.
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2013 (English)In: Physical Chemistry, Chemical Physics - PCCP, ISSN 1463-9076, E-ISSN 1463-9084, Vol. 15, no 46, 20189-20196 p.Article in journal (Refereed) Published
Abstract [en]

The molecular and electronic structures of aqueous I-3 and I ions have been investigated through ab initio molecular dynamics (MD) simulations and photoelectron (PE) spectroscopy of the iodine 4d core levels. Against the background of the theoretical simulations, data from our I4d PE measurements are shown to contain evidence of coupled solute-solvent dynamics. The MD simulations reveal large amplitude fluctuations in the I-I distances, which couple to the collective rearrangement of the hydrogen bonding network around the I-3(-) ion. Due to the high polarizability of the I-3(-) ion, the asymmetric I-I vibration reaches partially dissociated configurations, for which the electronic structure resembles that of I-2 + I-. The charge localization in the I-3(-) ion is found to be moderated by hydrogen-bonding. As seen in the PE spectrum, these soft molecular vibrations are important for the electronic properties of the I-3(-) ion in solution and may play an important role in its electrochemical function.

Place, publisher, year, edition, pages
2013. Vol. 15, no 46, 20189-20196 p.
National Category
Natural Sciences
URN: urn:nbn:se:uu:diva-212437DOI: 10.1039/c3cp52866aISI: 000326747200028OAI: oai:DiVA.org:uu-212437DiVA: diva2:677764
Available from: 2013-12-10 Created: 2013-12-10 Last updated: 2015-01-23Bibliographically approved
In thesis
1. Interfaces in Dye-Sensitized Solar Cells Studied with Photoelectron Spectroscopy at Elevated Pressures
Open this publication in new window or tab >>Interfaces in Dye-Sensitized Solar Cells Studied with Photoelectron Spectroscopy at Elevated Pressures
2014 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

With an increasing demand for renewable energy sources, research efforts on different solar cell technologies are increasing rapidly. The dye-sensitized solar cell (DSC) is one such technology, taking advantage of light absorption in dye molecules. The liquid based DSC contains several interesting and important interfaces, crucial for the understanding and development of the solar cell performance. Examples of such interfaces include dye-semiconductor, electrode-electrolyte and solute-solvent interfaces. Ultimately, complete interfaces with all these components included are of particular interest. One major challenge is to understand the key functions of these systems at an atomic level and one way to achieve this is to use an element specific and surface sensitive tool, such as photoelectron spectroscopy (PES). This thesis describes the use and development of PES for studying interfaces in the DSC.

The materials part of the thesis focuses on interfaces in DSCs studied with PES and the methodology development parts focus on methods to use PES for investigations of solvated heterogeneous interfaces of interest for photoelectrochemical systems such as the DSC. More specifically, beginning with standard vacuum techniques, dye molecules bound to a semiconductor surface have been studied in terms of energy level alignment, surface coverage and binding configuration. To increase the understanding of solvation phenomena present in the liquid DSC, liquid jet experiments have been performed in close combination with theoretical quantum calculations. As a step towards an in-situ method to measure a complete, functioning (in operando) solar cell, methodology development and measurements performed with higher sample pressures are described using new high pressure X-ray photoelectron spectroscopy techniques (HPXPS).

Place, publisher, year, edition, pages
Uppsala: Acta Universitatis Upsaliensis, 2014. 75 p.
Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology, ISSN 1651-6214 ; 1173
Dye-sensitized solar cells, interfaces, solvation, photoelectron spectroscopy, HPXPS, HP-HAXPES, liquid jet
National Category
Physical Chemistry
Research subject
Chemistry with specialization in Physical Chemistry
urn:nbn:se:uu:diva-230855 (URN)978-91-554-9022-5 (ISBN)
Public defence
2014-10-17, Häggsalen, Ångström laboratory, Uppsala, 10:15 (English)
Available from: 2014-09-25 Created: 2014-08-31 Last updated: 2015-01-23

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Eriksson, Susanna K.Siegbahn, HansHagfeldt, AndersRensmo, HåkanBjörneholm, Olle
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