Abstract
Reactions of PtO+ with O2 and CO2 and the collision-induced dissociation of PtO+ with Xe and of PtO2+ with Xe and Ar have been studied as a function of kinetic energy using guided ion beam tandem mass spectrometry in order to elucidate the thermochemistry of PtO2+. The kinetic energy dependences for these reactions show endothermic behavior except for Pt+·O2 + Xe → PtXe+ + O2. Analyses of the endothermic reaction cross sections yield the 0 K bond dissociation energies (BDEs) in eV (kJ/mol) of D0(OPt+−O) = 3.06 ± 0.07 (295 ± 7), D0(Pt+−O2) = 0.67 ± 0.05 (65 ± 5), D0(OPt+−CO) = 2.21 ± 0.10 (213 ± 10), D0(OCPt+−O) = 3.21 ± 0.12 (310 ± 12), and D0(Pt+−Ar) = 0.34 ± 0.09 (29 ± 9), reasonably consistent with available theoretical values. Combining the OPt+−O BDE measured here with literature data also yields the ionization energy of OPtO as 10.56 ± 0.48 eV. These data, along with complementary ab initio calculations, enable the potential energy surfaces for the activation of O2 by Pt+ to be mapped out in some de...
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