Modelling the optical, kinetic, and thermodynamic properties of soot precursor molecules
Repository URI
Repository DOI
Change log
Authors
Abstract
This thesis investigates the optical, kinetic, and thermodynamic properties of soot precursor molecules, namely polyaromatic hydrocarbons (PAHs), by applying \textit{ab initio} quantum chemical methods. In particular, density functional theory (DFT) is applied to study the properties of several different types of PAHs, including curved PAHs, localized
The optical band gaps (OBGs) of curved, cross-linked, and radical PAHs are computed using a DFT method corroborated with UV/Visible spectroscopy measurements. Curved PAHs are shown to increase the OBG due to hybridisation changes. In contrast,
The persistence of the polarity of curved aromatics in flame conditions is investigated by using DFT to calculate their barriers and rates of inversion. Curved PAHs above 11--15 (
The kinetics of seven-member ring formation in PAHs containing a five-member ring is investigated. Seven-member ring formation by the hydrogen-abstraction-acetylene-addition (HACA) mechanism is studied for two different PAHs, one closed shell and one resonance-stabilised-radical (RSR) PAH. The seven-member ring forms more quickly for the RSR PAH. Seven-member ring formation by four different bay closure processes is also studied. The rate constants determined for the pathways are then used in kinetic simulations in 0D homogeneous reactors. The hydrogen abstraction based pathway is seen to dominate until higher temperatures, where the carbene pathway takes over. The results suggest that seven-member ring formation in PAHs containing a five-member ring is possible at flame temperatures.
The impact of localized
The rate and equilibrium constants of cross-linking reactions between PAHs of various reactive edge types is computed. The forward rate constants confirms that reactions involving aryl