Bond dissociation energies of lanthanide sulfides and selenides

Resonant two-photon ionization spectroscopy has been employed to observe sharp predissociation thresholds in the spectra of the lanthanide sulfides and selenides for the 4f metals Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, and Lu. As these molecules possess a large density of electronic states near the ground separated atom limit, these predissociation thresholds are argued to coincide with the true 0 K bond dissociation energies (BDEs). This is because spin-orbit and nonadiabatic couplings among these states allow the molecules to predissociate rapidly when the BDE is reached or exceeded. The measured BDEs, in eV, are as follows: 5.230(3) (PrS), 4.820(3) (NdS), 4.011(17) (SmS), 3.811(8) (EuS), 5.282(5) (GdS), 5.292(3) (TbS), 4.298(3) (DyS), 4.251(3) (HoS), 4.262(3) (ErS), 5.189(3) (LuS), 4.496(3) (PrSe), 4.099(3) (NdSe), 3.495(17) (SmSe), 3.319(3) (EuSe), 4.606(3) (GdSe), 4.600(6) (TbSe), 3.602(3) (DySe), 3.562(3) (HoSe), 3.587(3) (ErSe), and 4.599(6) (LuSe). Through the use of thermochemical cycles, the 0 K gaseous heat of formation, Δ_fH_0K ^○, is reported for each molecule. A threshold corresponding to the onset of two-photon ionization in EuSe was also observed, providing the ionization energy of EuSe as 6.483(10) eV. Through a thermochemical cycle and the above reported BDE of the neutral EuSe molecule, the BDE for the Eu⁺-Se cation was also determined as D₀(Eu⁺-Se) = 2.506(10) eV. Bonding trends of the lanthanide sulfides and selenides are discussed. Our previous observation that the transition metal sulfides are 15.6% more strongly bound than the corresponding selenides continues to hold true for the lanthanides as well.