Reactions of CO and CO₂ with Gas-Phase Mo⁺, MoO⁺, and MoO₂⁺

Guided ion beam mass spectrometry is used to investigate the kinetic energy dependence of the bimolecular reactions of CO 2 and CO with Mo +, MoO +, and MoO 2 + . To obtain a more complete understanding of these systems, we probe MoO 2 + and the intermediates, Mo(CO 2 ) +, OMo(CO) +, OMo(CO 2 ) +, and O 2 Mo(CO) +, by collisional activation experiments with Xe. Thermochemical analyses of the reaction cross sections obtained in this study yield (in eV) D 0 (Mo + −CO 2 ) = 0.51 ± 0.07, D 0 (OMo + −CO 2 ) = 0.77 ± 0.03, D 0 (OMo + −CO) = 0.80 ± 0.08, D 0 (O 2 Mo + −CO) = 0.92 ± 0.17, and D 0 (OMo + −O) = 5.57 ± 0.14 eV. Additional features in some reaction cross sections are assigned to the formation of excited electronic states of the products, thereby allowing a speculative measurement of excitation energies for states of MoO + and MoO 2 + .