Bond dissociation energies of ScSi, YSi, LaSi, ScC, YC, LaC, CoC, and YCH.

Predissociation thresholds of the ScSi, YSi, LaSi, ScC, YC, LaC, CoC, and YCH molecules have been measured using resonant two-photon ionization spectroscopy. It is argued that the dense manifold of electronic states present in these molecules causes prompt dissociation when the bond dissociation energy (BDE) is exceeded, allowing their respective predissociation thresholds to provide precise values of their bond energies. The BDEs were measured as 2.015(3) eV (ScSi), 2.450(2) eV (YSi), 2.891(5) eV (LaSi), 3.042(10) eV (ScC), 3.420(3) eV (YC), 4.718(4) eV (LaC), 3.899(13) eV (CoC), and 4.102(3) eV (Y-CH). Using thermochemical cycles, the enthalpies of formation, ΔH°(g), were calculated as 627.4(9.0) kJ mol (ScSi), 633.1(9.0) kJ mol (YSi), 598.1(9.0) kJ mol (LaSi), 793.8(4.3) kJ mol (ScC), 805.0(4.2) kJ mol (YC), 687.3(4.2) kJ mol (LaC), 760.1(2.5) kJ mol (CoC), and 620.8(4.2) kJ mol (YCH). Using data for the BDEs of the corresponding cations allows ionization energies to be obtained through thermochemical cycles as 6.07(11) eV (ScSi), 6.15(13) eV (YSi), 5.60(10) eV (LaSi), 6.26(6) eV (ScC), 6.73(12) or 5.72(11) eV [YC, depending on the value of D(Y-C) employed], and 5.88(35) eV (LaC). Additionally, a new value of D(Co-C) = 4.045(13) eV was obtained based on the present work and the previously determined ionization energy of CoC. An ionization onset threshold allowed the measurement of the LaSi ionization energy as 5.607(10) eV, in excellent agreement with a prediction based on a thermochemical cycle. Chemical bonding trends are also discussed.