Bond dissociation energies of TiSi, ZrSi, HfSi, VSi, NbSi, and TaSi

Predissociation thresholds have been observed in the resonant two-photon ionization spectra of TiSi, ZrSi, HfSi, VSi, NbSi, and TaSi. It is argued that because of the high density of electronic states at the ground separated atom limit in these molecules, the predissociation threshold in each case corresponds to the thermochemical bond dissociation energy. The resulting bond dissociation energies are D₀(TiSi) = 2.201(3) eV, D₀(ZrSi) = 2.950(3) eV, D₀(HfSi) = 2.871(3) eV, D₀(VSi) = 2.234(3) eV, D₀(NbSi) = 3.080(3) eV, and D₀(TaSi) = 2.999(3) eV. The enthalpies of formation were also calculated as Δ_f,0KH°(TiSi(g)) = 705(19) kJ mol^-1, Δ_f,0KH°(ZrSi(g)) = 770(12) kJ mol^-1, Δ_f,0KH°(HfSi(g)) = 787(10) kJ mol^-1, Δ_f,0KH°(VSi(g)) = 743(11) kJ mol^-1, Δ_f,0KH°(NbSi(g)) = 879(11) kJ mol^-1, and Δ_f,0KH°(TaSi(g)) = 938(8) kJ mol^-1. Using thermochemical cycles, ionization energies of IE(TiSi) = 6.49(17) eV and IE(VSi) = 6.61(15) eV and bond dissociation energies of the ZrSi^- and NbSi^- anions, D₀(Zr-Si^-) ≤ 3.149(15) eV, D₀(Zr^--Si) ≤ 4.108(20) eV, D₀(Nb-Si^-) ≤ 3.525(31) eV, and D₀(Nb^--Si) ≤ 4.017(39) eV, have also been obtained. Calculations on the possible low-lying electronic states of each species are also reported.