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Formation of O 3 + upon Ionization of O 2 : The Role of Isomeric O 4 + Complexes
Author(s) -
Cacace Fulvio,
de Petris Giulia,
Rosi Marzio,
Troiani Anna
Publication year - 2002
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/1521-3765(20020816)8:16<3653::aid-chem3653>3.0.co;2-1
Subject(s) - chemistry , excited state , metastability , ion , ionization , oxygen atom , oxygen , ozone , photochemistry , analytical chemistry (journal) , computational chemistry , molecule , atomic physics , physics , organic chemistry
The course of the reaction of electronically and vibronically excited metastable O 2 + ( 4 Π u , ν ′) ions with O 2 , known to produce O 3 + , was examined by the joint application of computational and mass spectrometric methods. The results show that the reaction does not proceed by a direct mechanism and that it involves instead the intermediacy of the [O 2 + ( 4 Π u ) ⋅⋅⋅ O 2 ] and [O 3 + ( 4 A 2 ) ⋅⋅⋅ O] complexes, both theoretically characterized, and the latter one positively identified by structurally diagnostic mass spectrometric techniques. The reaction is a potential source of stratospheric ozone, in that O 3 + ions are known to undergo efficient charge exchange with oxygen to yield neutral O 3 .