The reaction of NH+⋅3 with H2S: Dependence on the translational and internal energy of NH+⋅3

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Abstract
The reactions of vibrationally and of kinetically excited NH+⋅3 ions with H2S were investigated using a tandem ion cyclotron resonance spectrometer. NH+⋅3 ions with internal energies ranging from 1–5 eV were generated by charge transfer reactions, whose energy partioning is known. The charge transfer reagents used included Ar+⋅, Kr+⋅, Xe+⋅, N2+⋅, CO+⋅2 , CO+⋅, and O+⋅2 . The ionic products formed in the reaction of excited NH+⋅3 with H2S were NH+4 , H2S+⋅ and H3S+. It is shown that the product distribution is sensitive to the NH+⋅3 internal energy. At low internal energies, NH+4 is the dominant product, while at 5 eV all three reaction products are of comparable intensity. Competition between formation of H2S+⋅ and H3S+ is effective only at NH+⋅3 internal energies above 2 eV. The total rate constant was found to be 6±2×10−10 cm3/s and appeared to be independent of the internal energy of NH+⋅3 . Kinetically excited NH+⋅3 ions were formed using ICR double resonance and the effect on product distribution and total rate constant in the reaction with H2S was studied. It is shown that kinetic energy exclusively drives the charge transfer channel. The total rate was independent of the NH+⋅3 kinetic energy in the energy range of the experiment.