Predissociation measurements of the bond dissociation energies of EuO, TmO, and YbO.

The observation of a sharp predissociation threshold in the resonant two-photon ionization spectra of EuO, TmO, and YbO has been used to measure the bond dissociation energies of these species. The resulting values, D(EuO) = 4.922(3) eV, D(TmO) = 5.242(6) eV, and D(YbO) = 4.083(3) eV, are in good agreement with previous values but are much more precise. In addition, the ionization energy of TmO was measured by the observation of a threshold for one-color two-photon ionization of this species, resulting in IE(TmO) = 6.56(2) eV. The observation of a sharp predissociation threshold for EuO was initially surprising because the half-filled 4f subshell of Eu in its ground state generates fewer potential energy curves than in the other molecules we have studied by this method. The observation of a sharp predissociation threshold in YbO was even more surprising, given that the ground state of Yb is nondegenerate (4f6s, S) and the lowest excited state of Yb is over 2 eV higher in energy. It is suggested that these molecules possess a high density of electronic states at the energy of the ground separated atom limit because ion-pair states drop below the ground limit, providing a sufficient electronic state density to allow predissociation to set in at the thermochemical threshold.