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

Michael H. Palmer, Philip J. Camp, Søren Vrønning Hoffmann, Nykola C. Jones, Ashley R. Head, Dennis L. Lichtenberger
2012 Journal of Chemical Physics  
The electronic states of 1,2,4-triazoles: A study of 1H-and 1methyl-1,2,4-triazole by vacuum ultraviolet photoabsorption and ultraviolet photoelectron spectroscopy and a comparison with ab initio configuration interaction computations Citation for published version: Palmer, MH, Camp, PJ, Hoffmann, SV, Jones, NC, Head, AR & Lichtenberger, DL 2012, 'The electronic states of 1,2,4-triazoles: A study of 1H-and 1-methyl-1,2,4-triazole by vacuum ultraviolet photoabsorption and ultraviolet
more » ... n spectroscopy and a comparison with ab initio configuration interaction 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-1,2,4triazoles, 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.
doi:10.1063/1.3692164 pmid:22401443 fatcat:lqu2c5hbevayli7ydxtvgxwa3i