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The aza-Payne reaction mechanism has been studied by theoretical DFT calculations. Three reaction pathways have been considered: two of them result in the formation of a three-membered ring, with either inversion (S N I, experimentally observed) or retention (S N R) at the substituted carbon. The third reaction path results in the formation of a fourmembered ring. The mechanisms were first studied in the gas phase with the bare anion (An − ). The role of the counterion (Li + ) was then analysed by study of the reaction with the neutral species (An − Li + ) in the gas phase. Results for the (An − Na + ) system are also presented. Finally, the role of the solvent (THF and H 2 O) was taken into account with the aid

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