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

Abstract

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, D0(EuO) = 4.922(3) eV, D0(TmO) = 5.242(6) eV, and D0(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 4f7 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 (4f146s2, 1Sg) and the lowest excited state of Yb is over 2eV 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.