Interstellar chemistry has been a growing field over the last several decades. There is particular interest on the nature and reactivity of interstellar molecules; most notably that of polycyclic aromatic hydrocarbons (PAHs). My thesis focused on the kinetics of unimolecular dissociation of small PAH and PAH-like molecules under interstellar conditions. PAHs (naphthalene (NAP), anthracene (ANT) and pyrene (PYR)), some dihydro- equivalents (1,2-dihydronapthalene (DHN) and 9,10-dihydrophenanthrene (DHP)) and a few other small aromatic organic molecules (indene (IND), ethynylbenzene (EB), propynylbenzene (PB) and benzocyclobutene (BCB)) were studied using imaging photo-electron photo-ion coincidence spectroscopy (iPEPICO) and electron impact mass spectrometry (MS); both mass analyzed ion kinetic energy spectrometry (MIKES) and collision induced dissociation (CID). Experiments were performed at different ionization energies to produce breakdown diagrams for the various fragments. These diagrams are then fit using RRKM theory to determine the zero Kelvin activation energy (E0) and the entropy of activation (Δ‡S); these results are then compared and discussed.
All these molecules were compared in order to try and find any overlying trends which could be applied to their role in the interstellar medium (ISM). It was determined that H loss was the dominant fragmentation channel, as it was the only dissociation channel common to the majority of molecules studied. It was also seen that organic fragment loss (C2H2, CH3 and C4H2) was only observed in smaller molecules which indicates that PAHs are not likely a source of these molecules. The small fragment molecules gave insight into the stability of closed ring structures, such as PAHs, through the comparison of the dissociation of closed and open structures. The dihydro-PAHs, selected as a probe to investigate the proposed catalytic role of PAHs in the formation of molecular hydrogen, yielded very interesting results. It was seen that these molecules would readily undergo isomerisation prior to dissociation. This added an unexpected level of difficulty to the calculations but quickly demonstrated how the presence of additional hydrogen atoms could greatly disrupt the dissociations, as it was not the simple process of removing them as it was originally believed.
The overall trend observed was that it is the structure, not the size, which has the dominating effect on the dissociation. Ions of similar structure behaved similarly, regardless of a change in mass; isomers, however, had radically different behaviours which can only be attributed to their differing molecular conformations. This observation could aid in the understanding of larger PAHs, those which are believed to exist in the ISM, and what role they may play in the chemistry of the universe.
| Identifer | oai:union.ndltd.org:uottawa.ca/oai:ruor.uottawa.ca:10393/31552 |
| Date | January 2014 |
| Creators | West, Brandi |
| Contributors | Mayer, Paul |
| Publisher | Université d'Ottawa / University of Ottawa |
| Source Sets | Université d’Ottawa |
| Language | English |
| Detected Language | English |
| Type | Thesis |
| Format | application/pdf |
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