Theoretical study on reactions of O3+ and N2: novel routes to dinitrogen bond activation

Plausible mechanisms for reactions of the ionized O3 with N2 are studied by DFT and electron correlation methods. Calculations show that formation of the primary products O2+ + N2O and N2O+ + O2 arises from an intermediate [O2⋯ON2]+ in the ground state and its charge-transfer excited state, respectively. New routes to NO2 + NO+ through an intermediate [ON2⋯O2]+ and to [ON⋯NO]+ + O2 via the reactions of O3+ with N2O are proposed. The former has a high barrier, while the latter is facile process with a small barrier of 20 kJ mol−1 and a huge exothermicity of 502 kJ mol−1.