Thermochemistry and mechanisms of the Pt+ + SO2 reaction from guided ion beam tandem mass spectrometry and theory.

The kinetic energy dependences of the reactions of Pt⁺ (²D_5/2) with SO₂ were studied using a guided ion beam tandem mass spectrometer and theory. The observed cationic products are PtO⁺ and PtSO⁺, with small amounts of PtS⁺, all formed in endothermic reactions. Modeling the kinetic energy dependent product cross sections allows determination of the product bond dissociation energies (BDEs): D₀(Pt⁺–O) = 3.14 ± 0.11 eV, D₀(Pt⁺–S) = 3.68 ± 0.31 eV, and D₀(Pt⁺–SO) = 3.03 ± 0.12 eV. The oxide BDE agrees well with more precise literature values, whereas the latter two results are the first such measurements. Quantum mechanical calculations were performed for PtO⁺, PtS⁺, PtO₂⁺, and PtSO⁺ at the B3LYP and coupled-cluster with single, double, and perturbative triple [CCSD(T)] levels of theory using the def2-XZVPPD (X = T, Q) and aug-cc-pVXZ (X = T, Q, 5) basis sets and complete basis set extrapolations. These theoretical BDEs agree well with the experimental values. After including empirical spin–orbit corrections, the product ground states are determined as PtO⁺ (⁴Σ_3/2), PtS⁺ (⁴Σ_3/2), PtO₂⁺ (²Σ_g⁺), and PtSO⁺ (²A′). Potential energy profiles including intermediates and transition states for each reaction were also calculated at the B3LYP/def2-TZVPPD level. Periodic trends in the thermochemistry of the group 9 metal chalcogenide cations are compared, and the formation of PtO⁺ from the Pt⁺ + SO₂ reaction is compared with those from the Pt⁺ + O₂, CO₂, CO, and NO reactions. [ABSTRACT FROM AUTHOR]