The electronic states of 1,2,3-triazole studied by vacuum ultraviolet photoabsorption and ultraviolet photoelectron spectroscopy, and a comparison with <em>ab initio</em> configuration interaction methods
Palmer, Michael H.3; Hoffmann, Søren Vrønning6; Jones, Nykola C.6; Head, Ashley R.5; Lichtenberger, Dennis L.5
1 Institute for Storage Ring Facilities - Aarhus (ISA), Faculty of Science, Aarhus University, Aarhus University2 Department of Physics and Astronomy, Faculty of Science, Aarhus University, Aarhus University3 University of Edinburgh4 Department of Physics and Astronomy - Institute for Storage Ring Facilities - Aarhus (ISA), Department of Physics and Astronomy, Science and Technology, Aarhus University5 The University of Arizona6 Department of Physics and Astronomy - Institute for Storage Ring Facilities - Aarhus (ISA), Department of Physics and Astronomy, Science and Technology, Aarhus University
The Rydberg states in the vacuum ultraviolet photoabsorption spectrum of 1,2,3-triazole have been measured and analyzed with the aid of comparison to the UV valence photoelectron ionizations and the results of ab initio configuration interaction (CI) calculations. Calculated electronic ionization and excitation energies for singlet, triplet valence, and Rydberg states were obtained using multireference multiroot CI procedures with an aug-cc-pVTZ [5s3p3d1f] basis set and a set of Rydberg [4s3p3d3f] functions. Adiabatic excitation energies obtained for several electronic states using coupled-cluster (singles, doubles, and triples) and complete active space self-consistent field procedures agree well with experimental values. Variations in bond lengths with the electronic state are discussed. The lowest energy UV band (∼5.5–6.5 eV) is assigned to three electronically excited states and demonstrates the occurrence of a nonplanar upper state on the low energy side. A UV photoelectron spectrum with an improved resolution yielded adiabatic and vertical ionization energies and reorganization energies for several of the lowest cationic states. As well as excitations to the s, p, d-Rydberg states are the excitations consistent with an f-series.
Journal of Chemical Physics, 2011, Vol 134, Issue 8