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Molecular Interaction in Aqueous Solutions: Effects of Temperature and Solutes on Surface Structure and Hydrogen Bonding in Water
Uppsala University, Disciplinary Domain of Science and Technology, Physics, Department of Physics and Astronomy, Molecular and Condensed Matter Physics.
2019 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Intermolecular forces in liquids can give rise to complex emergent structures, particularly in water, where hydrogen bonding causes the formation of extended networks, and surfaces, where intermolecular structures can be distinctly different from the bulk, leading to unique properties and behaviours. While such structures have been studied in detail, it is still relatively unknown how such structures respond and adapt to external changes to their environment. In this thesis, the structure formation behaviour, particularly at the water interface and in the hydrogen bond network, in response to external tunable parameters are investigated using a combination of spectroscopic techniques. Surface-sensitive X-ray photoelectron spectroscopy and Auger spectroscopy are employed to study samples of different sizes, ranging from single gas-phase water molecules where intermolecular interactions are negligible, to the infinite liquid bulk with its fully extended hydrogen bond network. Particular emphasis is placed on the influence of temperature on structural aspects of the studied systems, how they affect the hydrogen bond network as well as the surface enrichment of solutes.

The first part focuses on structure formation at surfaces, and in the case of solutes in water we find that elevated temperature increases the surface enrichment of halide ions, and a diverse set of behaviour for cations depending on the nature of the counter ion. These results are surprising since it was previously predicted that surface enrichment should decrease with temperature, and our results superficially appear to contradict the notion that any emergent structure should become washed out at higher temperature as entropy and disorder begin to dominate. In addition, results on the differences between the surface composition of wet and dry saline aerosols are presented, where we find notable structural differences linked to the different efflorescence points of salts during the drying process.

In the second part, results from studies exploring different aspects of the hydrogen bond network are presented, which are probed via the post-ionisation decay observed in the Auger spectrum. Firstly, the hydrogen bond network of water is studied at different temperatures and system sizes. We find both temperature, and confinement in the form of clusters, to measurably weaken the hydrogen bond network compared with the bulk liquid. Secondly, the influence of hydrophobic functional groups is studied in liquid methanol and mixed liquids containing the cryoprotectants glycerol and dimethyl sulfoxide. The presence of the hydrophobic groups leads to a fracturing of the intermolecular network into smaller domains of hydrophilic and hydrophobic groups.

Place, publisher, year, edition, pages
Uppsala: Acta Universitatis Upsaliensis, 2019. , p. 90
Series
Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology, ISSN 1651-6214 ; 1839
National Category
Atom and Molecular Physics and Optics
Identifiers
URN: urn:nbn:se:uu:diva-391083ISBN: 978-91-513-0721-3 (print)OAI: oai:DiVA.org:uu-391083DiVA, id: diva2:1343637
Public defence
2019-10-04, Room IV, Universitetshuset, Biskopsgatan 3, Uppsala, 09:15 (English)
Opponent
Supervisors
Available from: 2019-09-13 Created: 2019-08-18 Last updated: 2019-10-15
List of papers
1. Temperature Dependent Surface Propensity of Halide Salts
Open this publication in new window or tab >>Temperature Dependent Surface Propensity of Halide Salts
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(English)Manuscript (preprint) (Other academic)
National Category
Natural Sciences
Identifiers
urn:nbn:se:uu:diva-341963 (URN)
Available from: 2018-02-16 Created: 2018-02-16 Last updated: 2019-08-25
2. The surface of sea spray aerosol under scrutiny: An X-ray photoelectron spectroscopy study
Open this publication in new window or tab >>The surface of sea spray aerosol under scrutiny: An X-ray photoelectron spectroscopy study
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(English)Manuscript (preprint) (Other academic)
National Category
Natural Sciences
Identifiers
urn:nbn:se:uu:diva-341964 (URN)
Available from: 2018-02-16 Created: 2018-02-16 Last updated: 2019-08-18
3. Temperature dependence of X-ray induced Auger processes in water
Open this publication in new window or tab >>Temperature dependence of X-ray induced Auger processes in water
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(English)Manuscript (preprint) (Other academic)
National Category
Natural Sciences
Identifiers
urn:nbn:se:uu:diva-391079 (URN)
Available from: 2019-08-18 Created: 2019-08-18 Last updated: 2019-08-18
4. Signature of ultrafast proton transfer in the Auger spectrum of amorphous ice
Open this publication in new window or tab >>Signature of ultrafast proton transfer in the Auger spectrum of amorphous ice
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(English)Manuscript (preprint) (Other academic)
National Category
Natural Sciences
Identifiers
urn:nbn:se:uu:diva-341962 (URN)
Available from: 2018-02-16 Created: 2018-02-16 Last updated: 2019-08-18
5. Probing the Hydrogen-Bond Strength of Solvent Clusters using Proton Dynamics
Open this publication in new window or tab >>Probing the Hydrogen-Bond Strength of Solvent Clusters using Proton Dynamics
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(English)Manuscript (preprint) (Other academic)
National Category
Natural Sciences
Identifiers
urn:nbn:se:uu:diva-391080 (URN)
Available from: 2019-08-18 Created: 2019-08-18 Last updated: 2019-08-25
6. Competition between proton transfer and intermolecular Coulombic decay in water
Open this publication in new window or tab >>Competition between proton transfer and intermolecular Coulombic decay in water
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2018 (English)In: Nature Communications, ISSN 2041-1723, E-ISSN 2041-1723, Vol. 9, article id 4988Article in journal (Refereed) Published
Abstract [en]

Intermolecular Coulombic decay (ICD) is a ubiquitous relaxation channel of electronically excited states in weakly bound systems, ranging from dimers to liquids. As it is driven by electron correlation, it was assumed that it will dominate over more established energy loss mechanisms, for example fluorescence. Here, we use electron-electron coincidence spectroscopy to determine the efficiency of the ICD process after 2a(1) ionization in water clusters. We show that this efficiency is surprisingly low for small water clusters and that it gradually increases to 40-50% for clusters with hundreds of water units. Ab initio molecular dynamics simulations reveal that proton transfer between neighboring water molecules proceeds on the same timescale as ICD and leads to a configuration in which the ICD channel is closed. This conclusion is further supported by experimental results from deuterated water. Combining experiment and theory, we infer an intrinsic ICD lifetime of 12-52 fs for small water clusters.

Place, publisher, year, edition, pages
NATURE PUBLISHING GROUP, 2018
National Category
Physical Chemistry Condensed Matter Physics
Identifiers
urn:nbn:se:uu:diva-372335 (URN)10.1038/s41467-018-07501-6 (DOI)000451176100013 ()30478319 (PubMedID)
Funder
EU, Horizon 2020, 705515The Swedish Foundation for International Cooperation in Research and Higher Education (STINT)
Available from: 2019-01-07 Created: 2019-01-07 Last updated: 2019-08-18Bibliographically approved
7. Site-specific X-ray induced dynamics in liquid methanol
Open this publication in new window or tab >>Site-specific X-ray induced dynamics in liquid methanol
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2019 (English)In: Physical Chemistry, Chemical Physics - PCCP, ISSN 1463-9076, E-ISSN 1463-9084, Vol. 21, no 28, p. 15478-15486Article in journal (Refereed) Published
National Category
Atom and Molecular Physics and Optics
Identifiers
urn:nbn:se:uu:diva-391082 (URN)10.1039/C9CP02063B (DOI)000476603700022 ()31259327 (PubMedID)
Funder
Swedish Research Council, VR 2017-04162Swedish Research Council, VR 2018-00740Swedish Research Council, VR 2013-03940
Available from: 2019-08-18 Created: 2019-08-18 Last updated: 2019-09-24Bibliographically approved
8. Specific probing of the hydrogen bonding network in aqueous mixtures of glycerol and dimethyl sulfoxide
Open this publication in new window or tab >>Specific probing of the hydrogen bonding network in aqueous mixtures of glycerol and dimethyl sulfoxide
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(English)Manuscript (preprint) (Other academic)
National Category
Natural Sciences Atom and Molecular Physics and Optics
Identifiers
urn:nbn:se:uu:diva-391081 (URN)
Available from: 2019-08-18 Created: 2019-08-18 Last updated: 2019-08-18

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