Skip to main content
placeholder image

Ultraviolet photodissociation action spectroscopy of the N-pyridinium cation

Journal Article


Download full-text (Open Access)

Abstract


  • 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 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


  •   Hansen, Christopher (external author)
  •   Blanksby, Stephen J. (external author)
  •   Chalyavi, Nahid (external author)
  •   Bieske, Evan J. (external author)
  •   Reimers, Jeffrey R. (external author)
  •   Trevitt, Adam J.

Publication Date


  • 2015

Citation


  • Hansen, C. S., Blanksby, S. J., Chalyavi, N., Bieske, E., Reimers, J. R. & Trevitt, A. J. (2015). Ultraviolet photodissociation action spectroscopy of the N-pyridinium cation. Journal of Chemical Physics, 142 (1), 014301-1-014301-11.

Scopus Eid


  • 2-s2.0-84923807234

Ro Full-text Url


  • http://ro.uow.edu.au/cgi/viewcontent.cgi?article=3472&context=smhpapers

Ro Metadata Url


  • http://ro.uow.edu.au/smhpapers/2453

Has Global Citation Frequency


Start Page


  • 014301-1

End Page


  • 014301-11

Volume


  • 142

Issue


  • 1

Place Of Publication


  • United States

Abstract


  • 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 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


  •   Hansen, Christopher (external author)
  •   Blanksby, Stephen J. (external author)
  •   Chalyavi, Nahid (external author)
  •   Bieske, Evan J. (external author)
  •   Reimers, Jeffrey R. (external author)
  •   Trevitt, Adam J.

Publication Date


  • 2015

Citation


  • Hansen, C. S., Blanksby, S. J., Chalyavi, N., Bieske, E., Reimers, J. R. & Trevitt, A. J. (2015). Ultraviolet photodissociation action spectroscopy of the N-pyridinium cation. Journal of Chemical Physics, 142 (1), 014301-1-014301-11.

Scopus Eid


  • 2-s2.0-84923807234

Ro Full-text Url


  • http://ro.uow.edu.au/cgi/viewcontent.cgi?article=3472&context=smhpapers

Ro Metadata Url


  • http://ro.uow.edu.au/smhpapers/2453

Has Global Citation Frequency


Start Page


  • 014301-1

End Page


  • 014301-11

Volume


  • 142

Issue


  • 1

Place Of Publication


  • United States