Long-Lived Isomers of C$_{11}$H$_9^+$: New Experimental Insights from the PIRENEA Setup

Abstract

The dehydrogenated cation of methylated benzene is known to exist in two isomeric forms: benzylium and tropylium. Structurally similar forms have been proposed for the -H cations of methylated polycyclic aromatic hydrocarbons, but their spectroscopic characterization remains limited, and their photophysical properties are still poorly understood. Previous studies identified 2-naphthylmethylium and benzyltropylium as specific long-lived isomers of the -H fragment of methylnaphthalene cations. Here, we investigate the photodissociation spectroscopy and photoprocessing of gas-phase C$_{11}$H$_9^+$ ions in the visible range. Experiments are conducted using the versatile laboratory astrophysics setup PIRENEA, which enables studies over long timescales ($\sim$1000 s) and allows photoprocessing to be combined with ion-molecule reaction experiments. We confirm the presence of 2-naphthylmethylium and benzyltropylium and additionally identify 1-naphthylmethylium, previously undetected in experiments. Moreover, we present the first complete quantitative analysis of the relative abundances of these isomers and provide clear evidence of interconversion among the three long-lived species. These isomerization processes occur below the dissociation threshold, a finding supported by molecular dynamics simulations. The photophysical properties of C$_{11}$H$_9^+$ isomers -- including isomerization and fluorescence -- make them intriguing candidates for consideration in astrophysical environments exposed to mild UV irradiation (h$ν$ < 7 eV). Moreover, their detection via rotational spectroscopy in such regions is facilitated by their closed-shell electronic structure.