Indene (C9H8) is the only polycyclic pure hydrocarbon identified in the interstellar medium to date, with an observed abundance orders of magnitude higher than predicted by astrochemical models. The dissociation and radiative stabilization of vibrationally hot indene cations are investigated by measuring the time-dependent neutral particle emission rate from ions in a cryogenic ion-beam storage ring for up to 100 ms. Time-resolved measurements of the kinetic energy released upon hydrogen atom loss from C 9 H 8 + , analyzed in view of a model of tunneling through a potential energy barrier, provide the dissociation rate coefficient. Master equation simulations of the dissociation in competition with vibrational and electronic radiative cooling reproduce the measured dissociation rate. We find that radiative stabilization arrests one of the main C9H8 destruction channels included in astrochemical models, helping to rationalize its high observed abundance.

Several small polycyclic aromatic hydrocarbons (PAHs) with closed-shell electronic structure have been identified in the cold, dark environment Taurus Molecular Cloud 1. We measure efficient radiative cooling through the combination of recurrent fluorescence (RF) and IR emission in the closed-shell indenyl cation (C9H7+), finding good agreement with a master equation model including molecular dynamics trajectories to describe internal-energy-dependent properties for RF. We find that C9H7+ formed with up to Ec=5.85 eV vibrational energy, which is ≈2 eV above the dissociation threshold, radiatively cool rather than dissociate. The efficient radiative stabilization dynamics are likely common to other closed-shell PAHs present in space, contributing to their abundance.

The molecule, 2-cyanoindene, C₁₀H₇N (2CNI) is the only cyanosubstituted polycyclic aromatic hydrocarbon (PAH) detected in space, for which the hydrocarbon counterpart, indene, has also been observed in the same astrochemical environment—the molecular cloud TMC-1. In this study, based on experiments in two different laboratories, the collision and radiation-driven dissociation and cooling dynamics of the 2-cyanoindene monocations are investigated using one of the electrostatic ion-beam storage rings of the DESIREE facility, and the DESIRS beamline at the SOLEIL synchrotron radiation facility. The storage ring experiments quantify the balance between fragmentation and radiative cooling of the stored cations, while the synchrotron experiments characterize dissociation channels from the vacuum ultraviolet-induced dissociative photoionization of the neutrals. Recurrent fluorescence is shown to play an important role in the radiative stabilization of 2CNI⁺. The results from both sets of experiments are combined to obtain a self-consistent set of microcanonical rate coefficients for dissociation and radiative cooling that completely describe the near-dissociation threshold dynamics of 2CNI⁺ across the microseconds-seconds time range. This timescale is suitable for incorporation into astrochemical models of PAH growth and destruction lifecycles. This study extends its findings to different astrochemical environments by simulating the extent of fragmentation and the cascade emission spectra of 2CNI⁺ under varying interstellar radiation fields. These results indicate that radiative cooling enhances the resilience of 2-cyanoindene to harsh radiation conditions, suggesting that small cyano-PAHs may survive longer than previously assumed in a wider range of astrochemical environments, extending beyond cold, dark molecular clouds.