The role of some excited ions in laboratory ion–molecule reactions has been investigated, and their possible importance in the upper atmosphere considered. The mass spectrometer techniques of Aston banding and of comparing I.P. curves of parent and product ions have been applied to studies of collision-induced dissociation and charge exchange of oxygen and nitrogen in their parent gas. In every case studied, cross sections depended markedly upon the presence in the ion beam of ions in metastable or long-lived radiative states. In order that an ion reach the collision region, it had to have a mean lifetime greater than 3 μsec.The a 4Πu and b 4Σg excited states of O2+ were identified in the collision[Formula: see text]Higher states of O2+, which have not as yet been identified spectroscopically, were found in the collision[Formula: see text]The thresholds of these new states are 23.9, 27.9, 31.3, and 34.1 eV with an uncertainty ±0.2 eV. From the collision-induced dissociation of N2+, the A 2Πu and the [Formula: see text] states have been identified. Also, the reported transfer of the ν = 3 level of the B [Formula: see text] to the ν = 14 level of the A 2Πu was found.The cross section for 10/01 charged exchange of N2+ in N2 exhibited a marked decrease as excited-state ions diluted the beam. The 10/01 collisions of N+ in N2 and O+ in O2 exhibited an increase in cross section as metastables were added to the parent ion beam. The 10/20 reaction of O2+ in O2 was also observed to depend on excited O2+ ions.
The role of Li+ ions in the gas phase dehydrohalogenation and dehydration reactions of i-C3H7Br and i-C3H7OH molecules studied by radiofrequency-guided ion beam techniques and ab initio methods