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Title: Ultraviolet photodissociation action spectroscopy of the N-pyridinium cation

The S{sub 1}←S{sub 0} electronic transition of the N-pyridinium ion (C{sub 5}H{sub 5}NH{sup +}) is investigated using ultraviolet photodissociation (PD) spectroscopy of the bare ion and also the N{sub 2}-tagged complex. Gas-phase N-pyridinium ions photodissociate by the loss of molecular hydrogen (H{sub 2}) in the photon energy range 37 000–45 000 cm{sup −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 spectra. Most of the vibronic features are attributed to progressions of totally symmetric ring deformation modes and out-of-plane modes active in the isomerization of the planar excited state towards the non-planar excited state global minimum.
Authors:
;  [1] ;  [2] ; ;  [3] ;  [4] ;  [5]
  1. School of Chemistry, University of Wollongong, NSW 2522 (Australia)
  2. Central Analytical Research Facility, Queensland University of Technology, QLD 4000 (Australia)
  3. School of Chemistry, The University of Melbourne, VIC 3010 (Australia)
  4. School of Physics and Materials Science, University of Technology Sydney, NSW 2007 (Australia)
  5. (China)
Publication Date:
OSTI Identifier:
22415453
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 142; Journal Issue: 1; Other Information: (c) 2015 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; CATIONS; COMPLEXES; DEFORMATION; DISSOCIATION; ELECTRONIC STRUCTURE; EXCITED STATES; GROUND STATES; HYDROGEN; INTERNAL CONVERSION; ION-MOLECULE COLLISIONS; ISOMERIZATION; MOLECULAR IONS; PHOTOLYSIS; PHOTONS; PYRIDINES; ULTRAVIOLET RADIATION