Isomer effects on neutral-loss dissociation channels of nitrogen-substituted PAH dications

Abstract

We investigate two nitrogen-containing isomers of polycyclic aromatic hydrocarbons, quinoline and isoquinoline, of composition C9H7N in collisions with 7 keV O+ and 48 keV O6+ projectile ions. By employing ion–ion coincidence mass spectrometry, we determine branching ratios for H-loss, C2H2-loss, and HCN-loss dissociation channels of Q2+ and IQ2+. The overall contribution of HCN loss is found to be the dominant decay channel. A comparison with the results of a parallel experiment on naphthalene, the simplest PAH, reveals that HCN loss in both isomers has a higher propensity than the analogous C2H2 loss of naphthalene. The positional identity of the nitrogen atom in the two isomers mainly manifests in many-body fragmentation of their dications. Potential energy surfaces of Q2+ and IQ2+ are further computed to explore complete fragmentation mechanisms. Parent dications (Q2+ and IQ2+) are identified to isomerize via seven-membered ring structures before elimination of C2H2 and HCN. While prompt dissociation is the primary pathway, the dominant channel of each neutral-loss class also exhibits delayed fragmentation.