Abstract
The gas-phase reactivities of the transition-metal sulfides ScS+ and TiS+ are investigated with guided-ion beam (GIB) and Fourier transform ion cyclotron resonance (FTICR) mass spectrometry. In this work, we study the reactions of bare Sc+ and Ti+ ions with sulfur-transfer reagents, COS and CS2, and of the metal sulfides, ScS+ and TiS+, with oxygen-transfer substrates and with Xe to examine their collision-induced dissociation. The GIB experiments lead to several estimates for D0(M+−S). Further, the reaction MS+ + H2O → MO+ + H2S and its reverse are studied with GIB and FTICR. The equilibrium constants Keq derived from these measurements provide the most accurate values for D0(M+−S). Overall assessment of the results of ion−molecule reactions, collision-induced dissociations, and equilibrium measurements yields the 0 K bond dissociation energies D0(Sc+−S) = 4.97 ± 0.05 eV, D0(Ti+−S) = 4.74 ± 0.07 eV, D0(Sc+−CS) = 1.38 ± 0.08 eV, D0(Ti+−CS) = 1.60 ± 0.06 eV, and ΔfH0(TiOS+) = 9.04 ± 0.18 eV.
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