Aravind G

Nitrogen-bearing polycyclic aromatic hydrocarbons (PANHs) are ubiquitous in space. They are considered precursors to advanced biomolecules identified in meteorites. However, their chemical evolution into biomolecules in photodestructive astrophysical mediums remains a paradox. Here, we show that light can efficiently initiate the molecular mass growth of PANHs. Ultraviolet-photoexcited quinoline monomers, the smallest PANH, were observed to associate and intermolecular Coulombic decay between the associating monomers formed the cations of quinoline-dimer. Molecular rearrangements in the dimer cation lead to a dominant formation of cations heavier than quinoline. The enrichment of these heavier cations over all the other cations reveals the efficiency of this route for the mass growth of PANHs in space. This mechanism also leads to a highly reactive unsaturated PANH-ring via CH loss, a hitherto unknown channel in any photon-driven process. The occurrence of this efficient pathway toward complex molecules points to a rich chemistry in dense interstellar clouds.

A low-lying resonance in FeCN- anion was identified through abrupt changes in the spectral dependence of the photoelectron angular distribution. Non-Franck-Condon transitions from the resonance to the neutral FeCN (4 "), and the corresponding photoelectron angular distributions revealed that the resonance is a dipole scattering state. Significant thermionic electron emission was observed in the resonant photoelectron spectra, indicating a strong coupling of the resonance with the ground state of this triatomic anion and its competition over autodetachment. This low-lying resonance is identified to be an efficient pathway for the formation of FeCN- anion in the outer envelope of IRC+10216. The results in general reveal formation pathways in space for anions with low-lying resonances and large permanent dipole moment.

Intermolecular Coulombic decay (ICD) is a process whereby photoexcited molecules relax by ionizing their neighbouring molecules. ICD is efficient when intermolecular interactions are active and consequently it is observed only in weakly bound systems, such as clusters and hydrogen-bonded systems. Here we report an efficient ICD between unbound molecules excited at ambient-light intensities. On the photoexcitation of gas-phase pyridine monomers, well below the ionization threshold and at low laser intensities, we detected the parent and heavier-than-parent cations. The isotropic emission of slow electrons revealed ICD as the underlying process. π–π* excitation in unbounded pyridine monomers triggered an associative interaction between them, which leads to an efficient three-centre ICD. The cation resulting from the molecular association of the three pyridine centres relaxed through fragmentation. This below-threshold ionization under ambient light has implications for the understanding of radiation damage and astrochemistry. [Figure not available: see fulltext.]

The photoprocessing of astrophysically relevant small polycyclic aromatic hydrocarbon (PAH) molecules, namely, anthracene, phenanthrene, and pentacene, under intense UV field is experimentally studied to explore the formation of smaller ions upon their dissociative ionization and the effect of their size and structure on the dynamics of dissociative ionization. The molecules are UV processed in the multiphoton regime using a 266-nm nanosecond laser pulse. The dissociative ionization spectra at different laser intensities reveal distinct dissociation dynamics of these PAHs based on their size and structures.

Photoionization and dissociation of anthracene, phenanthrene, and pentacene in the multiphoton regime at 266 nm wavelength were performed. CHn+ (n = 4-6) ions were observed as fragments, and their yields as a function of laser intensity were studied. H-migration and "roaming" mechanisms leading to the formation of these fluxional ions from polycyclic aromatic hydrocarbons (PAHs) are proposed. The present results show higher photostability of PAHs with bent structure and suggest PAHs in the UV regions of interstellar medium as a prominent source for CHn+ (n = 4-6).