The early transition metal diatomic sulfides, MS, M = Sc, Y, Ti, Zr, Hf, Nb, and Ta, have been investigated using resonant two-photon ionization spectroscopy in the vicinity of their bond dissociation energies (BDEs). Due to the high density of vibronic states in this energy range, the molecular spectra appear quasicontinuous, and when the excitation energy exceeds the ground separated atom limit, excited state decay by dissociation becomes possible. The dissociation process typically occurs so rapidly that the molecule falls apart before a second photon can be absorbed to ionize the species, leading to a sharp drop in ion signal, which is identified as the 0 K BDE. The observed predissociation thresholds yield BDEs of 4.852(10) eV (ScS), 5.391(3) eV (YS), 4.690(4) eV (TiS), 5.660(4) eV (ZrS), 5.780(20) eV (HfS), 5.572(3) eV (NbS), and 5.542(3) eV (TaS). Utilizing thermochemical cycles, the enthalpies of formation, Delta H-f(0K)o(g), of 182.7(4.3) kJ mol(-1) (ScS), 178.3(4.2) kJ mol(-1) (YS), 293.1(16.7) kJ mol(-1) (TiS), 337.3(8.4) kJ mol(-1) (ZrS), 335.0(6.6) kJ mol(-1) (HfS), 467.0(8.0) kJ mol(-1) (NbS), and 521.5(2.1) kJ mol(-1) (TaS) are obtained. Another thermochemical cycle has been used to combine the previously measured M+-S BDEs with the M-S BDEs and atomic ionization energies to obtain the MS ionization energies of 6.44(5) eV (ScS), 6.12(8) eV (YS), 6.78(7) eV (TiS), 6.60(10) eV (ZrS), and 6.88(9) eV (NbS). Using this same cycle, we obtain D-0(Hf+-S) = 4.926(20) eV. The bonding trends of the early transition metal sulfides, along with the corresponding selenides, are discussed.
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