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Ultraviolet Photodissociation Action Spectroscopy Of The N-Pyridinium Cation, Christopher Hansen, Stephen J. Blanksby, Nahid Chalyavi, Evan Bieske, Jeffrey R. Reimers, Adam J. Trevitt

Faculty of Science, Medicine and Health - Papers: part A

The S1←S0 electronic transition of the N-pyridinium ion (C5H5NH+) is investigated using ultraviolet photodissociation (PD) spectroscopy of the bare ion and also the N2-tagged complex. Gas-phase N-pyridinium ions photodissociate by the loss of molecular hydrogen (H2) in the photon energy range 37 000-45 000 cm−1 with structurally diagnostic ion-molecule reactions identifying the 2-pyridinylium ion as the exclusive co-product. The photodissociation action spectra reveal vibronic details that, with the aid of electronic structure calculations, support the proposal that dissociation occurs through an intramolecular rearrangement on the ground electronic state following internal conversion. Quantum chemical calculations are used to analyze the measured …