Cerium (Ce) oxide, carbide, and carbonyl cation bond energies and the exothermicity of the Ce chemi-ionization (CI) reaction with atomic oxygen were investigated using guided-ion beam tandem mass spectrometry (GIBMS). The kinetic energy dependent product cross sections for reactions of Ce+ with O-2, CO, and CO2 and CeO+ with O-2, CO, Xe, and Ar were measured using GIBMS. For the reactions of Ce+ with O-2 and CO2, CeO+ is formed through an exothermic reaction, whereas CeO+ formation is endothermic in the reaction with CO. This reaction also forms CeC+ and CeCO+ is formed in the reaction of Ce+ with CO2, both in endothermic processes. Reactions of CeO+ with all four gases led to endothermic collision-induced dissociation as well as exchange reactions to form CeO2+ for the O(2 )and CO reactants. Bond dissociation energies (BDEs) at 0 K were determined through analyses of the kinetic energy dependent cross sections for all endothermic reactions. We determined that the BDEs of CeO+, CeC+, and CeCO+ are 8.46 +/- 0.15, 3.93 +/- 0.16, and >= 0.25 +/- 0.07 eV, respectively, where the CeO+ BDE is a weighted average of 6 independent 0 K threshold measurements. The CeO+ BDE is combined with the ionization energy (IE) of Ce to determine an exothermicity of 2.91 +/- 0.15 eV for the Ce + O -> CeO+ + e- chemi-ionization reaction. Combined with neutral BDEs from the literature, the thermochemistry determined here also provides IE(CeO) = 5.03 +/- 0.12 eV and IE(CeC) = 6.50 +/- 0.16 eV. Theoretical calculations for ground and some excited states were performed for CeO+, CeC+, and CeCO(+ )to provide insight into the bonding and a comparison with the experimentally determined BDEs for each molecule.
