Guided Ion Beam Study of Potential Energy Surfaces for Platinum Interactions with Nitrogen Oxides

Abstract

A guided ion beam tandem mass spectrometer is used to examine the kinetic energy dependence of reactions of Pt⁺ with NO, NO₂ and N₂O, and PtO⁺ with NO and NO₂, as well as collision-induced decomposition (CID) of PtO⁺ with N₂ and PtNO⁺ with Xe. Pt⁺ reacts with NO and NO₂ most efficiently by charge transfer, although oxygen atom transfer is also prominent for NO₂ and the dominant reaction with N₂O. Charge transfer is also the most efficient process observed for PtO⁺ + NO, whereas this ion reacts with NO₂ by inefficient oxygen atom transfer, and in the reaction of PtO⁺ with N₂, only simple CID and ligand exchange are observed. Analysis of the kinetic energy dependences for endothermic reaction cross sections yields the 0 K bond dissociation energies (BDEs) in eV (kJ mol⁻¹) of D₀(Pt⁺–N) = 3.35 ± 0.08 (323 ± 8), D₀(Pt–N) = 3.84 ± 0.10 (371 ± 10), D₀(Pt+–NO) = 3.13 ± 0.07 (302 ± 7) and D₀(Pt+–O) = 3.26 ± 0.07 (315 ± 7). The bond energy of D₀(Pt+–O) is consistent with our previous results and confirmed by results for nearly thermoneutral reactions here. Combining the BDEs of PtN⁺ and PtN measured here with literature data yields the ionization energy of PtN as 9.45 ± 0.13 eV.

Keywords

bond energies charge transfer collision-induced dissociation ionization energies oxidation tandem mass spectrometry thermochemistry

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