A Theoretical Study on the Reaction Mechanism of the Gas-Phase Decomposition of NO by NH3+ and NH4+

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High level ab initio calculations have been performed to study the mechanism of NO decomposition by NH3+ and NH4+ in the gas phase, NH3+ + NO → N2 + H3O+ and NH4+ + NO → N2H + H3O+. The density functional theory was used to search for possible reaction pathways. The multiconfigurational second-order perturbation (CASPT2) method is applied to the most energetically favorable pathways to obtain more accurate energy diagrams. NO reacts with NH3+ and NH4+ by producing nitrogen−nitrogen bound complexes and by donating protons/hydrogens to the O atom to weaken the N−O bond and to tighten the N−N bond. Maximum activation energies for these reactions were estimated as 55.3 and 77.3 kcal/mol.