Bond Dissociation Energies of Tungsten Molecules: WC, WSi, WS, WSe, and WCl

Resonant two-photon ionization spectroscopy was used to locate predissociation thresholds in WC, WSi, WS, WSe, and WCl, allowing bond dissociation energies to be measured for these species. Because of the high degree of vibronic congestion in the observed spectra, it is thought that the molecules dissociate as soon as the lowest separated atom limit is exceeded. From the observed predissociation thresholds, dissociation energies are assigned as D₀(WC) = 5.289(8) eV, D₀(WSi) = 3.103(10) eV, D₀(WS) = 4.935(3) eV, D₀(WSe) = 4.333(6) eV, and D₀(WCl) = 3.818(6) eV. These results are combined with other data to obtain the ionization energy IE(WC) = 8.39(9) eV and the anionic bond dissociation energies of D₀(W-C^-) = 6.181(17) eV, D₀(W^--C) = 7.363(19) eV, D₀(W-Si^-) ≤ 3.44(4) eV, and D₀(W^--Si) ≤ 4.01(4) eV. Combination of the D₀(WX) values with atomic enthalpies of formation also provides Δ_fH_0K° values for the gaseous WX molecules. Computational results are also provided, which shed some light on the electronic structure of these molecules.