Kinetics, thermodynamics, and ab initio calculations of HS 2O 7−(H 2SO 4) x ( x=1–3) cluster ions

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Temperature and pressure dependent decomposition kinetics of HS 2O 7 −(H 2SO 4) x ( x=1–3) cluster ions were measured in a quadrupole ion trap mass spectrometer. The kinetic data were analyzed with a master equation model to obtain the decomposition energies and energy transfer parameters for channels leading to elimination of sulfur trioxide and in some cases sulfuric acid. The ion cluster structures, vibrational frequencies and bond enthalpies were calculated ab initio at the HF/6-31+G(d) level of theory. The calculated bond energies agree well with the experimental results.