Dissociation of state-selected nitrogen trifluoride cations

Abstract

The dissociation of the nitrogen trifluoride ion (NF₃ ⁺) as a function of its initial internal-energy state has been studied by the photoelectron–photoion coincidence technique. The dissociation shows marked isolated-state behaviour. It follows essentially statistical predictions in the ground state and in the third excited state. There are larger releases of internal energy into translation for the dissociations from the first and second excited states and for these an impulsive model is proposed. The results are discussed in relation to the thermochemistry of the species involved and to the predictions of molecular-orbital calculations, especially by the semi-empirical MNDO method.