Abstract
The kinetic-energy dependence of SO2 activated by Os+ was studied by guided ion beam tandem mass spectrometry. Species observed in endothermic reactions were OsO+, OsO2+ or OsS+, and OOsS+. The kinetic energy-dependent cross sections were modeled to yield 0 K bond dissociation energies (BDEs) of 5.01 ± 0.06 eV (Os+-O), 5.15 ± 0.07 eV (Os+-O2), 4.50 ± 0.17 eV (Os+-S), and 4.22 ± 0.11 eV (Os+-SO). Among these BDE values, the values for OsO+ and OsO2+ agree with literature values and those for OsS+ and OOsS+ are novel measurements. Theoretical calculations were performed at a B3LYP/def2-TZVPPD level for all products, and additional calculations were performed for OsS+, OsO2+, and OsSO+ using the CCSD(T) level of theory, extrapolated to the complete basis set (CBS) limit, and def2-QZVPPD and aug-cc-pVxZ (x = T, Q, and 5) basis sets. These calculations indicate that the ground states of the products are 4Π5/2 (OsO+), 2B1 (OsO2+), 4Π5/2 (OsS+), and 2A″ (OOsS+) after including empirical spin-orbit corrections. The potential energy surfaces (PESs) for OsSO2+ intermediates, transition states, and all products were also investigated at the B3LYP/def2-TZVPPD level. The PESs show that none of the reactions have barriers in excess of the product endothermicities. Cross sections for OsO+ formation are compared to those from previous guided ion beam studies of related systems (Os+ + O2 and CO and Re+ + SO2) to evaluate their relative behaviors.
Published Version
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