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The N 3 + Reactivity in Ionized Gases Containing Sulfur, Nitrogen, and Carbon Oxides
Author(s) -
de Petris Giulia,
Cartoni Antonella,
Angelini Giancarlo,
Ursini Ornella,
Bottoni Andrea,
Calvaresi Matteo
Publication year - 2006
Publication title -
chemphyschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.016
H-Index - 140
eISSN - 1439-7641
pISSN - 1439-4235
DOI - 10.1002/cphc.200600245
Subject(s) - reactivity (psychology) , chemistry , ion , excited state , sulfur , reaction mechanism , nitrogen , ionization , carbon fibers , photochemistry , kinetics , mass spectrometry , qualitative inorganic analysis , inorganic chemistry , analytical chemistry (journal) , catalysis , atomic physics , organic chemistry , materials science , medicine , physics , alternative medicine , pathology , quantum mechanics , chromatography , composite number , composite material
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.