Application of chemical graph theory to PAH isomer enumeration and structure in laser desorption/ionization mass spectrometry studies of particulate from an ethylene diffusion flame

Our laboratory recently published data that showed that the PAH composition of soot can be exactly determined and spatially resolved by low-fluence laser desorption ionization, coupled with high-resolution mass spectrometry imaging [1] . This analysis revealed that PAHs of 239–838 Da, containing few oxygenated species, comprise the soot observed in an ethylene diffusion flame. In this paper, we demonstrate that the empirical formula of observed species can aid in the enumeration of isomers and places limits on their structures and thermodynamic stability. Specifically, chemical graph theory (CGT) shows that the vast majority of species observed in the sampled particulate matter may be described as benzenoid, consisting of only fused 6-membered rings. We apply CGT to determine the Dias Parameter, dS, for observed, individual PAH peaks and demonstrate that observed PAH species cluster near low dS, indicative of highly condensed structures, with relatively low populations of edge concavity (armchairs, bays, and fjords). Finally, we quantitatively explore the relative stability of PAH isomers using group-additivity estimates (for benzenoid structures) and those containing a single 5-membered rings using density functional theory. For the latter, we show that highly-condensed, benzenoid structures have lower free energy than those containing five-membered rings, with buried 5-membered rings showing the highest free energies.