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Studies of Intermolecular Interactions in Atmospheric Aggregates: From Molecular Clusters to Aerosols Open Access


Other title
intermolecular interactions
hydrogen-bonded clusters
carboxylic acid hydrates
rotational spectroscopy
secondary organic aerosol
soot aggregates
smog chamber experiments
Type of item
Degree grantor
University of Alberta
Author or creator
Schnitzler, Elijah G.
Supervisor and department
Jäger, Wolfgang (Chemistry)
Examining committee member and department
Jäger, Wolfgang (Chemistry)
Hanna, Gabriel (Chemistry)
Olfert, Jason S. (Mechanical Engineering)
Styler, Sarah (Chemistry)
Bertram, Allan K. (Chemistry, University of British Columbia)
Department of Chemistry

Date accepted
Graduation date
2016-06:Fall 2016
Doctor of Philosophy
Degree level
Intermolecular interactions dictate the fate and impact of atmospheric oxygenated organic compounds that form from the photo-oxidation of hydrocarbons. Here, intermolecular interactions in aggregates involving photo-oxidation products of aromatic precursors are examined using an interdisciplinary approach. Molecular-scale aggregates – in particular, complexes of water and carboxylic acids – were investigated using rotational spectroscopy. The lowest-energy structures of the monohydrates of two aromatic carboxylic acids, benzoic acid and o-toluic acid, were determined experimentally; the water and acid moieties hydrogen bond to give six-membered intermolecular rings. The percentage of each acid hydrated in the gas phase is predicted to be low, but these interactions are important for aromatic acids at the air-water interface of aqueous particles. The two lowest-energy isomers of the oxalic acid–water complex, a probable nucleation precursor, were also observed. In the lowest-energy isomer, water bridges the two acid groups and lowers the barrier to decarboxylation. In the other isomer, water hydrogen bonds to only one group and increases the barrier. For larger dicarboxylic acids, the latter topology is predicted to be the most stable, so water-catalysed enhancement of overtone-induced decarboxylation is plausible for only oxalic acid. The spectra, structures, and internal dynamics of four methyl- and dimethylnaphthalenes, small polycyclic aromatic hydrocarbons present in the atmosphere, were also investigated. Nano-scale aerosols – in particular, internally-mixed particles of black carbon and secondary organic aerosol – were investigated using smog chamber experiments. The morphological evolution of black carbon due to coatings of secondary organic aerosol is the same for a series of four aromatic precursors. The evolution of black carbon is found to be dependent on the coating surface tension; higher surface tensions lead to more compact black carbon particles, as intermolecular interactions between molecules in the coating become stronger. Based on the observed surface tension-dependence, the surface tension of secondary organic aerosol derived from m-xylene was determined, providing an essential constraint on global climate models. Cumulatively, these investigations provide insights into the fate and impact of oxidation products in the gas phase, at the air-water interface, and in the bulk aerosol phase.
This thesis is made available by the University of Alberta Libraries with permission of the copyright owner solely for the purpose of private, scholarly or scientific research. This thesis, or any portion thereof, may not otherwise be copied or reproduced without the written consent of the copyright owner, except to the extent permitted by Canadian copyright law.
Citation for previous publication
Schnitzler, E. G.; Jäger, W. Phys. Chem. Chem. Phys. 2014, 16, 2305-2314.Schnitzler, E. G.; Zenchyzen, B. L. M.; Jäger, W. Phys. Chem. Chem. Phys. 2016, 18, 448-457.Schnitzler, E. G.; Badran, C.; Jäger, W. J. Phys. Chem. Lett. 2016, 7, 1143-1147.Schnitzler, E. G.; Zenchyzen, B. L. M.; Jäger, W. Astrophys. J. 2015, 805, 141 (7 pp.).Schnitzler, E. G.; Dutt, A.; Charbonneau, A. M.; Olfert, J. S.; Jäger, W. Environ. Sci. Technol. 2014, 48, 14309-14316.

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