Polycyclic aromatic hydrocarbon-isomer fragmentation pathways: Case study for pyrene and fluoranthene molecules and clusters.

We report on measurements of the ionization and fragmentation of polycyclic aromatic hydrocarbon (PAH) targets in Xe20 + + C16H10 and Xe20 + + [C16H10]k collisions and compare results for the two C16H10 isomers: pyrene and fluoranthene. For both types of targets, i.e., for single PAH molecules isolated in vacuum or for isomerically pure clusters of one of the molecules, the resulting fragment spectra are surprisingly similar. However, we do observe weak but significant isomer effects. Although these are manifested in very different ways for the monomer and cluster targets, they both have at their roots small differences (<2.5 eV) between the total binding energies of neutral, and singly and multiply charged pyrene and fluoranthene monomers. The results will be discussed in view of the density functional theory calculations of ionization and dissociation energies for fluoranthene and pyrene. A simple classical over-the-barrier model is used to estimate cross sections for single- and multiple-electron transfer between PAHs and ions. Calculated single and multiple ionization energies, and the corresponding model PAH ionization cross sections, are given. [ABSTRACT FROM AUTHOR]