The N3+ Reactivity in Ionized Gases Containing Sulfur, Nitrogen and Carbon Oxides”.

The N3+ reactivity with SO2, N2O, CO2 and CO is studied by mass spectrometric techniques under a wide range of pressures ranging from 10-7 to 10-4 Torr. The N+ transfer features the N3+ reactivity with these simple inorganic molecules. The kinetics, reaction mechanism and the role of vibrationally excited ions are investigated by experimental and theoretical methods. Key distinguishing features of the N3+ reactivity are evidenced by comparison to N+ and N2+ ions, that mainly undergo charge exchange reactions. The N+ transfer to SO2 prompts formation of NO+ ions and neutral oxides NO and SO. The N+ transfer to N2O also leads to NO+ by a process not allowed by spin conservation rules. In both cases no reaction intermediate is detected, whereas CO2 and CO are captured to form the very stable NCO2+ and NCO+ ions. NCO2+ ions are characterized for the first time as strongly bound triplet ions of NOCO and ONCO connectivity. DFT and CCSD(T) computations have been carried out to investigate the structural and energetic features of the NCO2+ species and their formation process.