Study of Renner-Teller, spin-orbit, and Fermi-resonance interactions in X̃²Π(v₁v₂0) levels of NCO by stimulated emission pumping spectroscopy

We report extensive measurements of rovibronic levels in the 020/100 and 040/120/200 Fermi-resonant polyads of NCO. The levels were accessed by the technique of stimulated emission pumping spectroscopy in a supersonic free jet expansion following excitation of bands in the Ā²Σ ⁺-X̄²Π spectrum of the radical. The data were analyzed in terms of an effective Hamiltonian which explicitly included reference to all the possible vibronic levels of ²Π symmetry in the polyad under consideration. The effects of levels outside these were treated by perturbation theory. The model was successful in fitting the data close to the experimental measurement precision and the resulting parameters were interpreted in terms of the harmonic and anharmonic vibrational terms. The effective Renner-Teller coupling parameter in NCO varied with vibrational level; however, parameters describing the Fermi-resonance interaction were found to be constant for all the levels investigated.