Di Mino, Camilla;
(2023)
Weak Inter-Molecular Interactions in Bulk Liquids and at Liquid/Nanomaterial Interfaces.
Doctoral thesis (Ph.D), UCL (University College London).
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Abstract
Liquid systems are the ideal platform to study weak, competitive interactions. While molecular reorganization is inhibited in solids, molecules in liquids can rapidly rearrange. Understanding the average local molecular restructuring, in the presence of energetically comparable interactions, underpins this thesis. Here, hydrogen bonding, dipole-dipole interactions, and dispersion forces have been studied in a variety of bulk liquids and at the interface of a charged surface. The aim is to understand the molecular mechanisms from which macroscopic processes such as dissolution, dispersion, and solution stability are derived. The high hydrogen sensitivity, high spatial resolution, and highly penetrative nature of neutrons make them the ideal probe for studying hydrogen bonding and solution structures. Neutron diffraction combined with H/D isotopic substitution and molecular simulations via the empirical potential structure refinement method allowed the study weak OH···π and CH···O hydrogen bonding in the liquid state, revealing undiscovered cooperative interactions in the benzene-methanol prototypical system. The highly templated structuring found for benzene in methanol evolves when the π system is an alkene C=C bond or a substituted aromatic. In the latter case, due to the higher solubility in water of phenol, aniline, and p-nitrophenol than benzene, the aromatic hydrogen bonding can be tested directly with water, with important implications for our understanding of liquid water interactions. Lastly, the CH···O and the dipole-dipole interactions in tertiary amides play an important role in the dissolution of supercapacitor-like systems such as carbon nanomaterials. Testing these systems with the level of detail reached by neutron diffraction enabled a full characterisation of the restructuring of cyclic and planar amides at a charged π interface.
| Type: | Thesis (Doctoral) |
|---|---|
| Qualification: | Ph.D |
| Title: | Weak Inter-Molecular Interactions in Bulk Liquids and at Liquid/Nanomaterial Interfaces |
| Open access status: | An open access version is available from UCL Discovery |
| Language: | English |
| Additional information: | Copyright © The Author 2022. Original content in this thesis is licensed under the terms of the Creative Commons Attribution-NonCommercial 4.0 International (CC BY-NC 4.0) Licence (https://creativecommons.org/licenses/by-nc/4.0/). Any third-party copyright material present remains the property of its respective owner(s) and is licensed under its existing terms. Access may initially be restricted at the author’s request. |
| Keywords: | Neutron Diffraction, Molecular Simulations, Hydrogen Bonding, Monte Carlo |
| UCL classification: | UCL UCL > Provost and Vice Provost Offices > UCL BEAMS UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences > Dept of Physics and Astronomy |
| URI: | https://discovery.ucl.ac.uk/id/eprint/10180587 |
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