title: The N3+ reactivity in ionized gases containing sulfur, nitrogen, and carbon oxides.
abstract: The N(3)(+) reactivity with SO(2), N(2)O, CO(2), and CO is studied by mass spectrometric techniques under a wide range of pressures from 10(-7) to 10(-4) Torr. The kinetics, reaction mechanism, and role of vibrationally excited ions are investigated by experimental and theoretical methods. Key distinguishing features of the N(3) (+) reactivity are evidenced by comparison to N(+) and N(2)(+) ions, which mainly undergo charge-exchange reactions. The N(+) transfer to SO(2) prompts formation of NO(+) ions and neutral oxides NO and SO. The N(+) transfer to N(2)O also leads to NO(+) ions by a process not allowed by spin conservation rules. In both cases no reaction intermediate is detected, whereas CO(2) and CO are captured to form the very stable NCO(2) (+) and NCO(+) ions. NCO(2)(+) 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 NCO(2) (+) species and their formation process.
authors.affiliation: Dipartimento di Studi di Chimica e Tecnologia delle Sostanze Biologicamente Attive Università La Sapienza, P. le Aldo Moro 5, 00185 Roma, Italy. giulia.depetris@unirom1.it
authors.forename: Giulia
authors.initials: G
authors.lastname: de Petris
authors.forename: Antonella
authors.initials: A
authors.lastname: Cartoni
authors.forename: Giancarlo
authors.initials: G
authors.lastname: Angelini
authors.forename: Ornella
authors.initials: O
authors.lastname: Ursini
authors.forename: Andrea
authors.initials: A
authors.lastname: Bottoni
authors.forename: Matteo
authors.initials: M
authors.lastname: Calvaresi