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Søren Vrønning Hoffmann

The electronic states of 1,2,4-triazoles: A study of 1H- and1-methyl-1,2,4-triazole by vacuum ultraviolet photoabsorption and ultraviolet photoelectron spectroscopy and a comparison with ab initio configuration interaction computations

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  • Michael H. Palmer, University of Edinburgh, Storbritannien
  • Philip J. Camp, University of Edinburgh, Storbritannien
  • Søren Vrønning Hoffmann
  • Nykola C. Jones
  • Ashley R. Head, The University of Arizona, USA
  • Dennis L. Lichtenberger, The University of Arizona, USA
The first vacuum ultraviolet absorption spectrum of a 1,2,4-triazole has been obtained and analyzed in detail, with assistance from both an enhanced UV photoelectron spectroscopic study and ab initio multi-reference multi-root configuration interaction procedures. For both 1H- and 1-methyl-1,2,4-triazoles, the first ionization energy bands show complex vibrational structure on the low-energy edges of otherwise unstructured bands. Detailed analysis of these bands confirms the presence of three ionized states. The 6–7 eV VUV spectral region shows an unusual absorption plateau, which is interpreted in terms of the near degeneracy of the first two ionization energies, leading to a pseudo Jahn-Teller effect. The “fingerprint” of the ionization spectrum yields band origins for several Rydberg states. The configuration interaction study shows that although the equilibrium structure for the first cation is effectively planar, the second cation shows significant twisting of the ring system. Some calculated singlet electronic states also show skeletal twisting in which the ring C–H is substantially out of plane.
OriginalsprogEngelsk
TidsskriftJournal of Chemical Physics
Vol/bind136
Sider (fra-til)094310
Antal sider11
ISSN0021-9606
DOI
StatusUdgivet - 2012

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