A comparative laboratory study of soft X-ray-induced ionization and fragmentation of five small PAH cations

Abstract

Abstract The interaction between polycyclic aromatic hydrocarbon (PAH) radical cations and X-rays predominantly leads to photofragmentation, a process that strongly depends on PAH size and geometry. In our experiments, five prototypical PAHs were exposed to monochromatic soft X-ray photons with energies in the C K-edge regime. As a function of soft X-ray photon energy, photoion yields were obtained by means of time-of-flight mass spectrometry. The resulting near-edge X-ray absorption mass spectra were interpreted using time-dependent density functional theory (TD-DFT) with a short-range corrected functional. We found that the carbon backbone of anthracene$$^+$$ + (C$$_{14}$$ 14 H$$_{10}^+$$ 10 + ), pyrene$$^+$$ + (C$$_{16}$$ 16 H$$_{10}^+$$ 10 + ) and coronene$$^+$$ + (C$$_{24}$$ 24 H$$_{12}^+$$ 12 + ) can survive soft X-ray absorption, even though mostly intermediate size fragments are formed. In contrast, for hexahydropyrene$$^+$$ + (C$$_{16}$$ 16 H$$_{16}^+$$ 16 + ) and triphenylene$$^+$$ + (C$$_{18}$$ 18 H$$_{12}^+$$ 12 + ) molecular survival is not observed and the fragmentation pattern is dominated by small fragments. For a given excitation energy, molecular survival evidently does not simply correlate with PAH size but strongly depends on other PAH properties. Graphic abstract