Abstract
Reactions of Pt+ with O2, CO, and CO2 have been studied as a function of kinetic energy using guided ion beam tandem mass spectrometry in order to elucidate the bond energy of the PtO+ product. To further characterize the reaction of Pt+ with CO2, the reverse reaction of PtO+ with CO, and the collision-induced dissociation of PtCO2+ with Xe and Ar are also studied. In all cases, the kinetic energy dependences for these reactions show endothermic behavior except for PtO+ + CO → Pt+ + CO2 and PtCO2+ + Xe → PtXe+ + CO2. Analyses of the endothermic reaction cross sections yield the 0 K bond dissociation energies (BDEs) in eV (kJ/mol) of D0(Pt+−O) = 3.26 ± 0.07 (315 ± 7), D0(Pt+−CO) = 2.28 ± 0.05 (220 ± 5), D0(Pt+−CO2) = 0.62 ± 0.05 (60 ± 5), and D0(Pt+−C) = 5.46 ± 0.05 (527 ± 5), reasonably consistent with available theoretical values. Combining the PtO+ BDE measured here with literature data also yields the ionization energy of PtO as 9.52 ± 0.25 eV. These data, along with ab initio calculations at the B3LYP...
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